DDTea
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Halogenated Nitriles/Esters of Isocyanic Acid
I have read that compounds containing Halogens and a Cyanide group tend to be strong lachrymators- though not as toxic as Cyanides themselves. For
example, Cyanogen Chloride; it is a much stronger lachrymator than Hydrogen Cyanide, but it is markedly less toxic.
One compound that has really struck my interest though is Trichloroacetonitrile. It is a "severe lachrymator" according to its MSDS. I am
wondering if anybody has any experience with these compounds. In terms of their lachrymating ability, how do they compare to Halogenated Nitrates
(such as Chloropicrin or Tetrachloro Dinitroethane)?
Another compound that I am very interested in is Trichloromethyl Isocyanate...which I can find no information on. I'm not sure if this is
because it does not exist (i.e. it is terribly unstable), if it is rare, or if it just doesn't have any uses. It would seem to combine high
toxicity (because of the more reactive -C=N group) with severe lachrymatory power.
Now, the question of synthesis. Could such compounds be prepared in simple reactions similar to that of Chloropicrin? That is, reacting, say,
Acetonitrile with Sodium Hypochlorite?
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Nick F
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There's a nitrile synthesis in which an R-CX3 is reacted with NH3:
R-CX3 + NH3 --> R-CN + 3 HX
IIRC it takes place at elevated temperatures, ie by passing the vapours through a red-hot tube, perhaps over alumina or something, though I would have
to check to be sure...
Now, what if hexachloroethane was used...?
Chlorinating nitriles with NaOCl might also work, but not as well as with nitro compounds I think.
Does the Cl have to be on the same C as the -CN, or just anywhere?
"It would seem to combine high toxicity (because of the more reactive -C=N group) with severe lachrymatory power"
I would have thought it desirable to have non-toxic lachrymators and non-lachrymatory toxic compounds, not a combination of both these properties?
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DDTea
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That synth seems quite reasonable, actually; using vapors of Hexachloroethane.
In regards to the Cl and -CN, they can be anywhere in the molecule- not necessarily on the same Carbon  . However, I feel that Trichloroacetonitrile would be one of the easiest Halogen/Cyanide compounds to prepare.
However, as I said, Halogenated derivatives of Methyl Isocyanate seem very interesting. The trick, however, is first synthesizing Methyl
Isocyanate-which in itself is a very dangerous chemical. Do you suppose this would be done the same as with Nitriles? Say, HOCN + Dimethyl Sulfate?
When it comes to toxicity and lachrymatory powers, I believe it depends on the goal . For example, if a person is incapacitated b the lachrymation, they may be unable to don chemical protection. On the other hand, if they don't
know there is a chemical strike, they would not think to don the protection.
But for my purposes, I just take a strange interest in "nasties." There is just something about a strong lachrymator combined with high
toxicity that appeals to me  .
[Edited on 7-13-03 by Samosa]
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DDTea
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I am thinking a bit more clearly right now, so I will post once again.
That synthesis between an R-CX3 compound and NH3 is much like the synthesis between Chloroform and NH3 to produce Hydrogen Cyanide. I believe it does
involve the vapors of the R-CX3 though.
As for Hexachloroethane, I am not sure how that would react with the NH3.. Would it be:
C2Cl6 + NH3 --> CCl3CN + 3 HCl
or
C2Cl6 + 2 NH3 --> C2N2 + 6 HCl ?
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Nick F
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Well, some NC-CN will also be formed, but you can control that by using an excess of C2Cl6. Although actually, I think NC-CN would be easier to
seperate from the CCl3-CN than C2Cl6, plus it sounds like fun stuff, so maybe you might want to use an excess of ammonia.
C2Cl6's bp is an easy achievable 372*F, so that's not a problem.
If you have (mono/di/tri)chloroacetic acid, then you could prepare the ammonia salt, and successively dehydrate it to the amide, then the nitrile,
with P2O5, although this is perhaps a bit less OTC.
Substitution of polyhalo hydrocarbons with NaCN could work (in alcoholic solution), although it would likely leave you with a mixture of products
depending on exactly what you used and how you did it.
[Edited on 14-7-2003 by Nick F]
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