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Author: Subject: Picryl Azide and other Nitrophenyl Azides
Joeychemist
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[*] posted on 31-8-2005 at 19:54
Picryl Azide and other Nitrophenyl Azides


I’m looking for info about Nitrophenyl Azides and derivatives, namely 2,4,6 Trinitrophenyl Azide (Picryl Azide).

Trinitrophenyl Azide should be extremely energetic and could prove to be very interesting. Plus its preparation seems easy and straight forward and all the necessary regents and precursors are very easily attained.

o-nitrophenyl azide is prepared by reacting o-nitroaniline with sodium nitrite at 0°C to yield the diazonium salt which is then reacted with sodium azide at 0°C to yield o-nitrophenyl azide. o-nitrophenyl azide is then further nitrated to 2,4,6 Trinitrophenyl Azide with fuming nitric acid. (Or by reacting equi-molar amounts of Picryl chloride and Sodium Azide if you want to do it the easy way:P)

PATR 2700 states;

1•Azid-2,4,6.trinitro-benzene or Picrylazide
(called 2.4.6-Trinitro-diazobenzolimid or Pikrylazid
in Ger), (02 N)3C6H2.N3, mw 254.12, N
3 3.07%; yel prisms(from abs alc), mp 89-93°
(dec); soI in alc, benz, or chlf; insol in Iigroin
or petr eth. One method of prepn is by reacting
equi-molar quants of picryl chloride with NsN3
in aq alc soln. Other methods of prepn and props
are given in Refs 1, 2, 3 & 4
This compound is more sensitive to impact
than tetryl; it detonates on sl impact. it is an
expl more powerful and brisant than TNT (power
139% & brisance 132% TNT). it is unstable and
loses N when heated
Refs: l)Beil 5,279,(144) & [209] 2 )E.Schrader,
Ber 50, 777(1917) 3)H.Rathsburg, GerP 341961
(1921) 4)A.Korczynski & St.Namyslowski, BuII
Fr 35, 1186-94(1924)& CA 19,644(1925)


Any thoughts?



[Edited on 1-9-2005 by Joeychemist]
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J_O_H_N_Q
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[*] posted on 1-9-2005 at 21:09


Does it have to be made by forming the azide group while as o-nitroaniline?
Why not use trinitroaniline, nitrous acid, then make the azide group.

If I'm being stupid you'll have to forgive me, it been a couple monthes since I last looked over -NH2 + HNO2 reactions
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Joeychemist
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[*] posted on 3-9-2005 at 08:35


Thanks for your post John.

The question you asked is a good one and to tell you the truth I have no idea as to what the answer is, I just thought the reaction could be carried out at a smother pace doing it the way I previously stated. Hopefully someone else can clarify this? It would be much more practical and efficient if one could start from 2,4,6,-Trinitroanline.

It has been incredibly hard for me to find information about Picryl Azide, but that has now changed. I was searching google and came upon the following PDF;
http://rapidshare.de/files/4684281/halogen_and_nitro_phenyl_azide_derivatives.pdf.html

Quote:

The next compound targeted was 2,4,6-trintrophenyl azide which is an analogue of TNT
(trinitrotoluene) a commercial explosive thus making the target compound a possible HEDM.
2,4,6-trintrophenyl azide (picryl azide) was prepared by nitration of the previously prepared
o-nitrophenyl azide with fuming nitric acid.

The 2,4,6-trintrophenyl azide was isolated as a yellow powder and was recrystallised from
methanol to yield yellow needles with a melting point of 89-90°C, dec. The elemental
analysis for 2,4,6-trintrophenyl azide was in agreement with the theoretical values, (found C,
27.8 ; H, 0.8 ; N, 32.6 % calculated C, 28.4 ; H, 0.8 ; N, 33.1 %).The IR spectrum showed a
strong absorption at 2137 cm-1 for the asymmetric stretching vibration of the azide group, a
strong absorption at 1288 cm-1 for the symmetric stretching vibration of the azide and an
absorption at 623 cm-1 for the deformation of the azide group. The IR spectrum also showed
two weak absorptions at 3108 and 3096 cm-1 which are characteristic for C-H vibrations in an
aromatic ring, a strong absorption at 1603 cm-1 for the asymmetric stretching vibration of the
C-C bond in the aromatic ring, a strong absorption at 1536 cm-1 for the asymmetric stretching
vibration of the NO2 group and a strong absorption at 1351 cm-1 for the symmetric stretching
vibration of the NO2 group. The Raman spectra showed a peak at 2127 cm-1 for the
asymmetric stretching vibration of the azide group, a strong peak at 1287 cm-1 for the
symmetric stretching vibration of the azide. The Raman spectrum also showed a peak at 1556
cm-1 for the asymmetric stretching vibration of the C-C bond in the aromatic ring, a peak at
1537 cm-1 for the asymmetric stretching vibration of the NO2 group and a strong peak at 1350
cm-1 for the symmetric stretching vibration of the NO2 group. The ab initio calculation of the
vibrational frequencies for 2,4,6-trintrophenyl azide was carried out at the self consistent HF
level of theory using a 6-31G(d) basis set with a scaling factor of 0.89 [26].


[Edited on 3-9-2005 by Joeychemist]
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Rosco Bodine
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[*] posted on 3-9-2005 at 08:51


One of my ideas for an experiment has been to nitrate moth crystals of the paradichlorobenzene variety , to form
trinitrodichlorobenzene and then to react this in moist acetone with sodium azide to
produce a trinitrodiazidobenzene .
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[*] posted on 19-9-2005 at 07:09


Quote:
Originally posted by Rosco Bodine
One of my ideas for an experiment has been to nitrate moth crystals of the paradichlorobenzene variety , to form
trinitrodichlorobenzene and then to react this in moist acetone with sodium azide to
produce a trinitrodiazidobenzene .


Have you done any more with this idea? I was reading a journal article which dealt w/ paradichlorobenzene & it's a very interesting compound. - And damn cheap to purchase.




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Rosco Bodine
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[*] posted on 19-9-2005 at 13:29


No I haven't tried it . IIRC , the trinitro derivative of paradichlorobenzene is easily made using the sodium nitrate and sulfuric acid nitration method which has been described in a patent . But there are some extremely irritating and toxic fumes which could be problematic during such a nitration , beyond what is that problem already bad enough for nitrations of other aromatics . So it has not been high on my list of experiments to do , as it would be something like nitrating tear gas in order to obtain trinitroteargas :D

Not having actually done the nitration I can't guarantee that this concern has validity , but it could be about right .
It could be wargas dangerous to fool around with , so I have left it alone for now . Maybe someday I'll get around to it .
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Joeychemist
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[*] posted on 19-9-2005 at 14:46


I can’t say that performing that procedure wouldn’t be dangerous, but no serious war gases would be produced during that procedure unless the PDCB were to have its Cl striped from it and attached to a side chain attached to the benzene ring (which is unlikely to happen during a standard nitration). When halogens are attached directly to the benzene nucleus the lachrymatory power significantly decreases but when the halogen is attached to a side chain the lachrymatory power is very great (this is generally the rule, of course there are exemptions to the rule, like Chloroacetophenone, one of the most powerful lachrymators known). The addition of a Nitro group to a molecule which has a Halogen attached to a side chain will significantly increase the lachrymatory power of that substance! So worst case scenario is you create a nasty toxic explosive (That could be carcinogenic) or you create one of many possible deadly substances which can suffocate you with one breath or can slowly poison you by exposure, either way, you can’t really win.

:P


[Edited on 19-9-2005 by Joeychemist]
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