Chisholm
Hazard to Self
Posts: 62
Registered: 2-4-2017
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Mood: No Mood
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Chloropicrin + Cu powder
Picryl chloride in ethanol, treated with a suspension of fine copper, reacts to form hexanitrobiphenyl. Styphnyl chloride
(1,3-dichloro-2,4,6-trinitrobenzene) in ethanol, treated with copper, forms a polymer of picryl units of varying length before dropping out of
solution.
So what would occur if chloropicrin (trichloronitromethane) in alcohol solution were treated with copper powder?
Ordinarily, I would just try it myself, but chloropicrin is incredibly irritating to work with, and any polymerization reactions would be very
exothermic and possibly dangerous. Thus, I decided to come here first.
Since there's only one carbon, no carbocations would be formed. Additionally, at neutral or mildly acidic pH, no SN2 would occur.
What I could see happening is two chloropicrin molecules coming in contact with a copper surface at the same time and very close together;
Cu(II) chloride would form and the spare electrons would form a bond between the chloropicrin molecules.
But that's just a guess; I don't actually have any data to back that up. And subsequent reactions of 1,2-dinitro-1,1,2,2-tetrachloroethane would be
hard to predict, since it's possible that they would simply eliminate to form 1,2-dinitro-1,2-dichloroethylene rather than further polymerize. And
once you have an unsaturated bond connected to four electron-withdrawing groups, all kinds of crazy things can start to happen.
[Edited on 5-18-2017 by Chisholm]
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PHILOU Zrealone
International Hazard
Posts: 2893
Registered: 20-5-2002
Location: Brussel
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Mood: Bis-diazo-dinitro-hydroquinonic
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Yep I also wondered what would happen...
I have thought about it already...
-Dimerization and formation of dinitroacetylen or halogenated dérivatives
-Linear 1D polymerization products of dihalodinitroethylene (-CCl(NO2)-CCl(NO2)-)n
-Linear 1D polymerization products of dinitroacetylene (polydinitroacetylene) (-C(NO2)=C(NO2)-)n (*)
-Planar 2D polymerization products of dinitroacetylene (=C(NO2)-)n (**)
-Curved Planar 2D polymerization products of dinitroacetylen (=C(NO2)-)n --> Pernitrobulkminsterfullerenes (**)
(*) This eventuality will lead to spontaneous decomposition via nitro-nitrite rearrangement and high sensitivity to shock, storage unstability and
hydrolysis succeptibility (see Hexanitrobenzene properties to get a feeling but here should be worst)...the NO2 group onto the next carbon via the sp2
C=C bond is an electron withdrawing group and destabilizes the first NO2...
(-C(NO2)=C(NO2)-)n <--==> (-C(-NO2)=C(-O-N=O)-)n
(-C(-NO2)=C(-O-N=O)-)n + H2O <--==> (-C(-NO2)=C(-OH)-)n + HO-N=O
(-C(-NO2)=C(-OH)-)n <--==> (-CH(-NO2)-C(=O)-)n what is equal to (-CHNO2-CO-)n
Then you have three possibilities:
a) (-CHNO2-CO-)n <--==> (-CHONO-CO-)n
(-CHONO-CO-)n + H2O <--==> (-CHOH-CO-)n + HONO
The CO group is also EWG and may destabilize the viccinal nitro to nitrite and increase its hydrolysis to an alcohol setting nitrous acid free; Do not
forget that each CHNO2 is surrounded by 2 EWGs C=O...; alternatively the CH will be more acidic and may thus vafor Henry type of reaction between the
C=O and the CH-NO2 to make 2D or 3D polymers alcohols or unsaturated nitrocompounds.
b) (-CHNO2-CO-)n + HONO <--==> (-C(NO)(NO2)-CO-)n --water--> CH2(NO)(NO2) + H2O + CO2 (H2O + CO2 = H2CO3)
The nitrosonium N=O from nitrous acid will be very happy to react with a CH-NO2 to form a nitroso-nitrocompound ; the later will be more than happy to
hydrolyse to get nitroso-nitromethane.
c) (-CHNO2-CO-)n + H2O <--==> CH3-NO2 + H2O + CO2
Maybe the nitroketon will be already reactive enough to split off nitromethane from the nitroketon.
(*) It is to be noted that the density of Hexanitrobenzene reaches the 2,01 gr/ccm and VOD is close to 10 km/s.
Such a 1D Linear polymer like this should display a density over the 2,01 (2,35 if I calculated it right) and thus must be even faster for its VOD
(close to 12 km/s).
(**) Such a 2D planar polymer (not the curved ones) displaying a network of colladed cyclohexane rings will be stable and less prone to nitro-nitrite
rearrangement, less shock sensitive and must be even denser than the 1D polymer (over 2,65 and maybe arround 3,1 gr/ccm if I calculated it right) and
the related VOD will of course be tremendous (between 13 to 15 km/s).
[Edited on 18-5-2017 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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