Better than Chloropicrin

[nbk2000]

Symmetrical tetrachlorodinitroethane, obtained by the action of fuming nitric acid on tetrachloroethylene...forms crystals melting at 142° to 143° C...[and] is a much more powerful lachrymator than chloropicrin.


War Gases, Sartori, pg 163-164

Tetrachloroethylene, also known as perchloroethylene, is very conveniently available as an aerosol brake cleaner at <$3/pound (neat), in CRC Brakleen Brake Parts Cleaner[/brand name]. Got mine at Wal-Mart.

Obtaining Fuming Nitric acid shouldn't be a problem for anyone here, either. Wonder if an acid/nitrate mix would work...

Being a crystalline solid, as well as being 'much more powerful than chloropicrin', brings interesting possibilities to mind, such as absorbing it into silica gel and grinding it into fine dust for use as a persistant area-denial agent, same as the CS powder formulations.

No solvents were mentioned, but if there's any suitabily volatile ones available, then spraying would create microfine particulates as the solvent evaporated off, leaving the crystals suspended in the air.

Assuming that 'much more powerful than chloropicrin' means a 5x increase in potency, than that'd put 500gms of TCDNE at being capable of contaminating 50,000 cubic meters (the size of your average Wal-Mart. :)) to an insupportable level (10mg/CuM), which would likely be an order of magnitude higher than that needed to cause irritation to delicate soccer-mom membranes, thus starting a stampede in the herd.

And in the back of War Gases it's listed as a 'Toxic Irritant', which would, to me, indicate that it's at least as toxic as chloropicrin, if not more so, making it a lethal agent in a high enough concentration which, if it's toxicitiy is on par with its irritant capacity (compared to chloropicrin), would make it as toxic as phosgene (at least).

Not too shabby considering its humble orgins as break cleaning fluid.

The original articles would need to be reviewed to get an idea of the actual production procedure, yields, and toxicity, prior to proceeding with anymore suppositions.

Mr. Somosa, in his topic about dinitroacetylene (over at SM), came very close to seeing this but somehow missed it.

I did not. :p

[b]REF:
Ber., 1902, 35, 1529
J. Phys. Chem., 1919, 23, 578.

(CCl2NO2)2, MW 257.8
1mg/L=95ppm
1ppm=.0105mg/L

[teshilo]

Reaction between chloroform and nitric acid for create PS require high pressure and temperature and time (48 hours). :rolleyes: :rolleyes: May be and in case with tetrachloroethylene also ....

[megalomania]

As requested, 1 Chemische Berichte and 1 Journal of Physical Chemistry coming right up... I also did a Chemical Abstracts search for the particulars.

I had to get the Berichte articles from microfilm, which scans and prints pages of photo-copier quality, so there is not much I can do about my scans of the pages. The J. Phys article is hot off the presses from ACS.

The only reference to tetrachlorodinitroethane in Chemical Abstracts (since the late 60s) is in some Japenese journal:

Phase transition of hexa-substituted ethane having nitro-group. Nishizaka, Tadashi; Katuragawa, Fumio; Sawada, Kazuhiro; Oda, Tsutomu; Koide, Tsutomu. Lab. Phys. Chem., Osaka Kyoiku Univ., Osaka, Japan. Chemistry Express (1987), 2(5), 257-60. CODEN: CHEXEU ISSN: 0911-9566. Journal written in Japanese.

O2NCMe2CMe2NO2 (I) undergoes solid phase transition at 322 and 388 K. O2NCCl2CCl2NO2 (II) undergoes solid phase transition at 241 K. The crystal structure of I is triclinic below 322 K, and is a body-centered cubic above 388 K. The structure of II is a body-centered cubic lattice above 241 K


CAS name: 1,1,2,2-tetrachloro-1,2-dinitro-ethane
Also called: 1,1,2,2-Tetrachloro-1,2-dinitroethane and NSC 110925
Formula: C2 Cl4 N2 O4
CAS#: 67226-85-1

I hope someone will translate the German text into English, please. The J. Phys. Chem. article mentions an earlier synthesis reference in Chem Ber, namely Ber. deutsch. chem. Ges., 2, 326 (1869). Way back in volume 2, now that is old, I don't know if my microfilm goes back that far. The Phys article at least outlines the procedure quite well, and goes on to explain the method of the Chem Ber article (the 1902 one) improved on the yield using the older procedure. I don't think relying on the older literature will be necessary because it looks like the Phys. article is based on the old methods, and does quite a good job of explaining the synthesis. Well, I don't need to explain it, read for yourself...

[nbk2000]

8x more irritant, and 6x more toxic, than chloropicrin.

:D

[MrSamosa]

I am now in a position where I have much better access to resources and materials than I could have imagined a few months ago.

I don't have the specific reference on me, but I found a few papers regarding Tetrachlorodinitroethane. It takes the form of crystals which decompose when exploded (as by artillery shells). However, it becomes quite nasty when dissolved in Chloropicrin. It's probably soluble in other organic solvents too, but I like the idea of using toxic solvents for toxic agents. The result would essentially be "super chloropicrin."

Synthesis is straight forward but finicky. The reaction vessel tends to build up pressure (there is a risk of explosion) and leak off NOx and the product can decompose.

I'm going off memory right now; I'll see what I can do for you in the coming days :)

EDIT: oh silly Samosa; I forgot to download Mega's references before posting. That's the paper I'm talking about.

[FUTI]

AFAIR alkene is easy to convert to double nitro compound. There is some industrial procedure that use NOx to do it resulting in approx 60% yield of mixed Nitro and nitroso compound. That one should be easy to convert to dinitro derivative. I hope this help in your search for the mighty stench guys ;) sometimes you cry sometimes you laugh :D be positive and laugh as much as you can.

[tmp]

Now on my FTP under "CHEMISTRY - ORGANIC". Credit to Mega -
Thanks for attaching the PDF !