TetrachloroDinitro-Ethane

[MrSamosa]

For the sake of ease, TetrachloroDinitro-Ethane from here on will be referred to as "TCDNE."

Anyhow, this is a compound of particular interest because of its absolutely vicious lachrymating properties. In the book War Gases, it was compared to Chloropicrin. It was stated that it was 6 times as toxic and 8 times more lachrymating than Chloropicrin :eek: . I'm not sure why, but for a long time I had made the assumption that Chloropicrin was the most potent lachrymator... well, this throws that theory out of the water :D .

Now, the synthesis. Usually, it is prepared by the reaction between Tetrachloro-Ethylene and Nitrogen Peroxide. However, there are more convenient ways... Tetrachloro-Ethylene and Nitric Acid works just fine too.

Still, this is not good enough for me. Tetrachloroethylene is not a chemical that is easy to obtain, for I cannot find any OTC uses for it. Unlike some other Halocarbons, this unfortunately is NOT a refrigerant. As such, I am pursuing alternate methods for synthesizing this compound...

Do you suppose that this could be prepared by reacting Sodium Hypochlorite with 1,2-Dinitroethane, similar to the reaction between Sodium Hypochlorite and Nitromethane?

[simply RED]

Can you give me a link to the book "war gasses"?
I can find Cl2C=CCl2 at no cost here but still don't know what do use it for.
It may also be good for smoke with Zn powder and ZnO. Instead of Cl3C-CCl3.
another synthesys will be:
CClH2-CClH2 + 2NaNO2 = NO2CH2-CH2NO2 + 2NaCl
NO2CH2-CH2NO2 + 4Cl2 hv = NO2CCl2-CCl2NO2 + 4HCl
Use quarz lamp to lite at NO2CH2-CH2NO2 and bubble Cl2.
NO2CH2-CH2NO2 is dangerous explosive with sensitivity slightly less then NG, said to be unstable.

[a_bab]

Tetrachloro Etylene is called also perchloroethylene and you may find it as a stain remover, as it disolves greases really well. I also can get it really cheam (around 1 dollar/litter) and I was asking myself last week what it could be usefull for :D

Still bromoacetone is a very good option for me as a lacrymator. I didn't knew about the fact that chloropicrine is considered as the best lacrymator. It seems that I didn't payed enough attention when I read the War Gasses.

Simply Red, the book is quite large, unless you have a broad band. It's 25,5Mb and you can get it from the FTP.

[MrSamosa]

The method that I thought up today is as follows...

1- Reaction between Acetylene and Nitric Acid to form 1,2-Dinitroethane

HC= CH + 2 HNO3 --> NO2-C-C-NO2

2- Reaction between 1,2-Dinitroethane and Sodium Hypochlorite

NO2-C-C-NO2 + 4 NaOCl --> NO2Cl2-C-C-Cl2NO2 + 4 NaOH

Basically, it's the same as yours, Simply RED, except that I chose to use Sodium Hypochlorite as opposed to straight Chlorine. I don't like to work with Chlorine, not just because of its irritating properties, but also because its smell gives me a headache. Now, no guarantee that my way works...but this way works to replace the Hydrogens on Nitromethane with Chlorines to produce Chloropicrin.

I don't know if Chloropicrin is the best lachrymator, but I had always thought that it was. However, one reason that it was so popular during WW1 was because of its low cost and amazing ease of production.

Also, thanks for the info about Tetrachloroethylene; I really had no clue where to find it :) . But, now that that problem is out of the way, this could be the way that gives the best yield- Tetrachloroethylene and Nitric Acid:

Cl2C=CCl2 + 2 HNO3 --> Cl2NO2-C-C-NO2Cl2

[nbk2000]

Check automotive brake and carb cleaners. Some of them have perchloroetylene in them.

Chloropicrin is rather weak compared to CS or brombenzyl cyanide., but it's easier to make, and very stable.

[Hystrix]

I think it can't be raw material for TCDNE since it's very reactive. Even basicity of glass is enough for its decomposition. The reaction is similar to this:
NO2-CH2-CH2-NO2 + NaOH = NaNO2 + H2O + CH2=CH-NO2
So you can't chlorinate it with hypochlorite (but chlorination with Cl2 may be possible).
By the way, dinitroethane is strong explosive (stronger than picric acid). However, it was not applied due to its unstability.

EDIT: 1,2-dinitroethane is a solid with mp 39 deg. C and it's less sensitive than picric acid.

[simply RED]

mp 39
I was right for the quarz lamp ... :P

[nbk2000]

I found this product in an automotive store.

http://www.crcindustries.com/images/photos/05018.jpg

Main ingredient is perchloroethylene (AKA tetrachlorethylene). Cost: $3/20oz

You can search the msds for it at www.crcindustries.com Product #05018

[MrSamosa]

I was in ACE Hardware the other day, re-stocking on chemicals and buying some new ones. While in the Automotive section, I came across 2 or 3 degreasers...and a "general degreaser." None of them listed what ingredients were in them. However, they did contain labels warning that, "This product contains a chemical known to the state of California to cause cancer." Seeing as Perchloroethylene is a Carcinogen, would it be fair to guess that it is the hazardous ingredient in these degreasers? Or would it be best not to make that assumption?

[Mr Cool]

Well, since they're probably cheap you could pick up a can and test. Without doing that I would not assume anything. I can't think of many common np solvents that California does not consider carcinogenic.

[nbk2000]

Unless you have an msds for it, assume it's NOT perchloro.

The degreasers could have any number of things in them, like acetone/MEK/xylene/toluene/DCM/etc.

California lists all sorts of things as carcinogens, 'cause of some lawsuit over it back in the 80s. :rolleyes:

[jfk]

I think it most likely that the degreaser has toluene or xylene in it, as both can de grease an engine quite quickly and are both carcinogenic in their own right.