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Sauron
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I obtained the full (25 page) DTIC document reporting on Fluorochem's preparation of FDNE via CFNM.
They flatly state the idea came from the Russian literature and cite two articles by same principal investigator whose name shows up consistently
through two decades of Novichok-related publications.
Unfortunately, this report was written at a point when the Naval Research Lab had redirected Fluorochem's labors, and prior to their eventual success,
so for details we still must rely on their patents.
They do say that commercial 1,2-dichloro-1,2-difluoroethylene and also same prepared by then by Locke's method, were contaminated by 10% 1,1-difluoro
isomer which if nitrated would generate a highly toxic product.
So I suppose their success came only after preparing this substrate without the byproduct.
[Edited on 10-2-2007 by Sauron]
Attachment: FDNE.pdf (958kB)
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Sauron
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A treasure trove of information on the halogenated nitromethanes and nitrosomethanes is to be found in PATR 2700. I have extracted the two key
sections and combind them in a pdf attached below.
Volume 3 p.40-41
Volume 8 p.89-104
Specifically, chlorofluoronitromethane is found there.
Chlorofluoronitrosomethane can be prepapred from that by mild reduction, but AFAIK either compound reacts in same fashion with OP compounds, so there
is no particular need to do that reduction unless you like blue colored compounds.
We were told that these dihaloformaldoxines have the general structure
-O-N=C(X)-y where X and Y are F, Cl, Br, or a stable pseudohalogen like CN. In the examples shown to us X and Y are different but we cannot disallow
the possibility of X=Y. Therefore the number of possible combinations are trivial to calculate, and most of these combinations are now documented here
as the immediate precursor. The only exceptions are the ones containing -CN.
The preparative methods are diverse and the literature extends back to the 19th century. An examination of this ought to allow us to do a better job
of filling in the remaining blanks.
Picatinny's interest of course is in energetics applications such as the longstanding interest in fluorodinitroethanol. The long exploited process for
this came to a halt in 1970 when the Swedish plant making nitroform (TNMe) blew up.
Obviouly though a different US Army arsenal two states to the south of Dover NJ also has a keen interest in these dihalonitromethanes and
nitrosomethanes.
Fascinating reading. Enjoy!
[Edited on 11-2-2007 by Sauron]
Attachment: ExtractfromPATR2700.pdf (1.7MB)
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Sauron
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The mining of PATR 2700 for preps, references etc on the halonitromethanes, nitrosomethanes and related compounds is proving to be interesting and
productive.
Some of these are proving to be easy to prepare (or so it appears on paper).
I'll present a full report when I am done digging.
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Sauron
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Nitrosomethane itself is fascinating.
In monomeric form it is a blue gas.
But it is usually isolated as its dimer Me-N(O)=(O)N-Me which is a solid, which rearranges to the gas when heated above its melting point. Further
heating produced trimeric formaldoxime.
At ordinary temperatures nitrosomethane slowly changes into the formaldoxime cyclo(-N(OH)-CH2-}3, a six membered heterocycle C3H9N3O3
Most preps are by UV irradiation of tert-butyl nitrite via a methyl radical process. Yields are variable but in general not high. tert-butyl nitrite
isn't cheap but can be prepared from cheaper materials.
Nitrosomethane and its dimer can be halogenated by the elements into dihalofonitrosomethanes such as dichloronitrosomethane and dibromonitrosomethane.
Difluoronitosomethane is not so easy.
Both cis and trans isomers are possible.
Nitrosomethanes are easily oxidixed to nitromethanes.
Nitromethanes may is some cases be reduced to nitrosomethanes but overreduction gives methylamines.
Freshly prepared formaldehyde oxime hydrochloride (formaldoxime monomer) can be reacted with nitrosyl chloride in cold Et2O to give
chloronitrosomethane I am hoping that this compound can be fluorinated or that one of the chlorines on dichloronitrosomethane can be exchanged for
F.That wiuld give the important chlorofluoronitrosomethane.
Nitrosyl chloride is made from sodium nitrite and conc HCl per Inorg.Syn. vol 4.
Formldehyde oxime monomer hcl from hydroxylamine hydrochloride and formalin soln. The oxime is extracted with ether after salting out with CaCl2.
No need for messing about with carbonyl chloride fluoride, the above procedures don't appear to be anything like that hazardous.
The halogenated nitrosomethanes are doubtless irritants and should be assumed to be toxic and carcinogenic but, normal precautions ought to suffice.
[Edited on 13-2-2007 by Sauron]
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Sauron
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Here's another interesting prep, this one for monohalonitromethanes starting from readily available diethyl malonate:
1. The malonic ester is nitrated in high yield to diethyl nitromalonate.
2. The nitromalonate is halogenated. In the literature example the reagent is perchloryl fluoride gas, but I am sure for Cl and Br much less exotic
reagents will suffice.
3. The product is saponified and decarboxylated to the halonitromethane.
Fluoronitromethane is stable below 5 C and the best yields were only 32% but the F compound is a difficult one.
So, diethyl malonate could be used instead of socium chloroacetate to prepare unsubstituted nitromethane, and ordinary conc nitric acid used instead
of sodium nitrite. Ought to be useful for those of you who have expressed difficulty in obtaining sodium nitrite. Details and references on request.
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Sauron
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I am well along with literature searching to flesh out the information gleaned from PATR 2700 ("Federoff's") and extend it to present.
That covers the halogenated nitromethanes and nitrosomethanes.
What remains are the halonitroacetonitriles and halonitrosoacetonitriles. Some haloacetonitriles are commercial products.
ISIS/Draw's nomenclature routine did not 'like' the tautomer of the nitrosoacetonitriles with C=N bond although this is probably the stabler form
since it is conjugated to the nitrilo group. However it accepted the other tautomer with N=O bond and named it correctly as nitrosoacetonitrile.
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Sauron
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There's an obscure derivative of phosgene with one Cl replaced by -CN.
It is a liquid with b.p. 120 C and is prepared by dehydrating and chlorinating ethyl oxamate with phthaloyl chloride. See Sartori, "The War Gases"
p.58 and ref 1.
(ethyl oxamate is the ethyl ester of oxamic acid, the half amide of oxalic acid.)
NC-C(=O)Cl
The oxime if this NC-C(=NOH)Cl would be very very close to
NC-C(=N-O)Cl the nitroso cpd or NC-C(-NO2)Cl the chlorocyanonitromethane
Another route might be via methyl or ethyl nitroacetate (commercial products or easily prepared from nitromethane).
nitroacetate to nitroacetamide to nitroacetonitrile (aka cyanonitromethane). Start with a halonitroacetate and you end with same structure as from
ethyl oxamate.
We are told the Russians use acetonitrile as a starting point, and also chloropicrin, but I still do not find any evidence that this is true. It is
true that the intermediates and precursors are substituted nitromethanes/nitrosomethanes and some can be regarded as substituted acetonitriles, but
that does not necessarily mean getting to these directly.
The nitroacetic esters by the way are tools in peptide synthesis, my primary synthetic interest. Very interesting that they turn up in novichok
chemistry as well.
Formyl fluoride is known, so is carbonyl fluoride. So doubtless cyanoformyl fluoride may exist (may even be know.) Same with cyanoformyl bromide
although it might be less toxic and less stable.
Wonder why iodine is absent from the novichoks? Carbonyl iodide is known but extremely unstable with a -80 C temp of decomposition. The same holds for
the oxime, very low stability. Also reduced toxicity.
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Sauron
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Diethyl oxalate (commercially available and cheap) is treated with the calculated amount of ammonium hydroxide in ethanol to give ethyl oxamate.
EtOC(=O)C(=O)-NH2
This is treated with phthaloyl chloride, which dehydrtaes the amide to nitrile, cleaves the ester and chlorinates the acyl group to produce
cyanoformyl chloride, oily liquid, bp 120 C at normal pressure.
Cl-C(=O)-CN
Hit that carbonyl with hydroxylamine hcl and what have you got?
Cl-C(=NOH)-CN
which is awfully akin to the target compound
Cl-C(-N=O)-CN
In fact at the right pH I's expect these to be tautomers.
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hbx53
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Enquiry
How can we increase the persistence capacity of dimethylmercury?
One of Novichok product consists of Acetonitrile and ______ ? Can you tell the second one?
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Sauron
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I'm not inclined to increase persistence of dimethylmercury. I'd rather reduce it to about zero.
DETRITUS.
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Sauron
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Newer Developments on Novichoks and Folient Project
The Allen Reaction appears to be pertinent to the novichoks and "Folient" Project and was first described in JACS 79, 3071-3073 (1957). I will post
this here shortly. Various web pages mis-cite this paper as JACS 79, 3071 (1975) and give no DOI or author.
The DOI of the correct paper is 10.1021/ja01569a022
The title is: :
"Phosphorus (V) Acid Esters of Oximes"
which ought to be enough to make anyone who has read the posts upthread sit up and take notice.
The abstract states:
"Alkyl esters of trivalent phosphorus acids react with a-halogenated nitro compounds to give alkyl halide and oxime esters of the corresponding
pentavalent phosphorus acids."
[Edited on 3-7-2008 by Sauron]
Attachment: ja01569a022.pdf (421kB)
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Sauron
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Way upthread we examined some purported Novichok structures reported by "Samosa"
Now we have more details on the reaction and precursors.
The starting esters are glycol esters of PF3 or PFCl2 acid halides of phosphorous acid H3PO3 The first structure shown below is precursor to Novichok
A-230 and the second, to Novichok A-234.
These are reacted at subzero temperatures with dichlorofluoronitrosomethane in dry Et2O and on warming to O C or above rearrange to the open chain
esters.
The following are precursors to the compounds described by Samosa.
[Edited on 3-7-2008 by Sauron]
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ScienceSquirrel
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Personally I wonder how much of the Novichoks program is the product of the fevered imaginations of intelligence operatives and defence contractors
out to get their hands on a wodge of Uncle Sam's dollars.
Many years ago there was a compound called red mercury; what it was, even if it contained mercury at all was in doubt, what was not in doubt was that
it was the hottest thing in defence since bullets.
It could;
a) render an aeroplane completely invisible to radar
b) 'focus' the neutron flux in a A bomb so you could make one the size of a hand grenade
and a lot more besides.
A lot of money and time was wasted on red mercury and I reckon there are a few old KGB men relaxing in their dachas on the Black Sea coast courtesy of
the CIA ninnies.
However no verifiable sample of red mercury has ever been produced.
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Sauron
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Having been main mover in the debunking of "red mercury" on this forum, I am here to assure you that no parallel exists in regard to novichoks.
Red mercury was the invention of scam artists and confidence tricksters not intelligence services. They were trying to fleece the sorts of people with
lots of cash and an interest in buying supposed nuclear materials for bomb making.
The evidence for the reality of the novichok Folient Project in former USSR is massive. Russian scientists have been arrested, imprisoned and
prosecuted for whistle blowing about this. The main sources are emigre former scientists. Russian journal articles confirm much of what they are
saying. Ans American officialdom, which was quick to debunk red mercury as a fraud, is silent on the novichoks. Several well known authorities on CW
have included novichoks in their books. It is not mere Wikipedia claptrap.
See the attached document.
[Edited on 3-7-2008 by Sauron]
Attachment: novichoks2.doc (61kB)
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Sauron
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Here are the unstable intermediate of the reaction of gluorinated phospholane shown above and dichlorofluoronitrosomethane. The lower structure is the
final novichok identified as A-240.
The same compound could be built from 2-chloroethanol, POCl3, KF, and phosgene oxime. The last is a substance the Russians have more experience with
than anyone as they mass produced it as a chemical weapon in WWII.
A fluorinated derivative of chloropicrin would also work.
[Edited on 3-7-2008 by Sauron]
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ScienceSquirrel
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Perhaps it would be unsporting of me to point out that red mercury was at it's height during the late eighties - early nineties.
Neither Wikipedia nor this board existed at the time and most of the stuff written about it is in the dead tree library.
There was definitely a good healthy dose of scam about it but quite who was scamming whom never really became clear.
Anyway I remember plenty of other 'intelligence' stories. What about the stuff that was being pedalled in the run up to the invasion of Iraq?
If you believed the line that Bush and Blair were running Sadam Hussein had enough nasties to render the whole Mediteranean basin free of life.
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Sauron
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Use the search engine, o unsporting one. There was some damned fool who started a thread about red mercury and some similarly imaginary isotopes on
this forum last year and citing pages from Wikipedia. THAT is what I was referring to. I take note that you are very new here and can't really be
expected to have read everything that has gone before your arrival. That, however, does not mean that the forum only started when you got here.
Anyway this thread is about the chemistry of the novichoks and not about red mercury at all. If you don't wish to stay on topic kindly go elsewhere.
[Edited on 4-7-2008 by Sauron]
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ScienceSquirrel
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| Quote: | Originally posted by Sauron
Diethyl oxalate (commercially available and cheap) is treated with the calculated amount of ammonium hydroxide in ethanol to give ethyl oxamate.
EtOC(=O)C(=O)-NH2
This is treated with phthaloyl chloride, which dehydrtaes the amide to nitrile, cleaves the ester and chlorinates the acyl group to produce
cyanoformyl chloride, oily liquid, bp 120 C at normal pressure.
Cl-C(=O)-CN
Hit that carbonyl with hydroxylamine hcl and what have you got?
Cl-C(=NOH)-CN
which is awfully akin to the target compound
Cl-C(-N=O)-CN
In fact at the right pH I'd expect these to be tautomers. |
Perhaps you could explain how these would be tautomers as they do not have the same number of atoms.
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ScienceSquirrel
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Also could you give a reference for the reaction of a compound of the type RCOCl reaction to form an oxime.
I would normally expect the formation of RCONHOH via elimination of HCl from the transition intermediate.
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Sauron
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It's immaterial.
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Sauron
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You misreprersent the structure
The compound in question is a derivative of phosgene, and perhaps you have heard of phosgene oxime? Or the oxime of carbonyl chloride fluoride?
-CN is a psuedohalogen.
Actually, phthaloyl chloride will not dehydrate ethyl oxamate that way. The old paper is wrong. This was proven when the compound ClC(=O)-CN was
prepared by other means and identified by modern instrumental methods. Its physical constants were nothing like the material obtsined from ethyl
oxamate and phthaloyl chloride. In fact as you might expect, the bp of the mixed carbonyl was intermediate between those of phosgene and carbonyl
cyanide.
Also the mixed nitrile is not stable and disassiciates to a mixture of phosgene and carbonyl cyanide, the symmetrical compounds, in a few days.
I did a seperate thread on this errata in the old literature. It will be fun one of these days to prepare ethyl oxamate and react it with phthaloyl
chloride, and see just what that product really is. But it is not Cl-C(=O)-CN.
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ScienceSquirrel
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I would say that it is very far from immaterial.
Some of your chemistry is fine but some of it would have left my PhD supervisor with his jaw hanging open!
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Sauron
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You resurrected a post how old? to argue over a trivial point and then attack me personally? You haven't earned the right. Not by a long shot.
The point is immaterial because the novichok compounds (real or not) are reported to be prepared NOT from the oximes but from the
alpha-halonitromethanes and nitrosomethanes, and the appropriate trivalent phosphorus compound.
The discussion in the early part of this thread a year and some months gone is therefore, rendered moot. Redacting it is a waste of time.
You are just doing your best to derail this thread. You will not succeed.
[Edited on 4-7-2008 by Sauron]
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ScienceSquirrel
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I have heard of phosgene oxime but you do not make it by reacting phosgene with hydroxylamine.
Reaction of ammonia or an amine produces the corresponding urea derivative,
(NH2)2CO
and
(RNH)2CO
I would expect hydroxylamine to form
(NHOH)2CO
Do you have to earn the 'right' to question someone's chemistry round here?
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Sauron
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The first few posts in this thread were written eighteen months ago and concerne a mention in Sartori's THE WAR GASES (in the forum library), q.v.) of
the reaction between ethyl oxamate and phthaloyl chloride to produce the mixed Cl-C((=O)-CN.
Subsequently I learned that Sartori's cited paper was in error. The assymetrical carbonyl has been prepared by reaction of phosgene and HCN under
autogenous pressure, and characterized by instrumental analysis unavailable to the author Sartori quoted. His high boiling product therefore cannot be
the assymetrical carbonyl, which actually has the expected bp between phosgene and carbonyl cyanide, the symmetrical analogs.
As the editing time on this forum is limited I cannot go back and correct anything in those year and a half old posts. I only mentioned that old paper
because it appeared to be pertinent to Samosa's document which indicated that the formaldoxime moiety in novichoks could include a pseudohalogen such
as -CN on the carbon.
As it turns out those novichoks are prepared not from the phosgene oximes but from the halogenated nitromethanes or nitrosomethanes, analogs of
chloropicrin, or chloropicrin itself.
Chloropicrin etc are unpleasant irritants and lachrymators but, phosgene oxime is deadly, and at the least will blind very quickly.
These phosphorus (V) acid oxime esters therefore arise indirectly by the Allen reaction and not via the oxime, although oximes have been used to prove
structure in certain relatively nontoxic cases.
So, thanks for pointing out that phosgene oxime is not prepared from phosgene and hydroxylamine. But the matter of the oximes as far as this thread is
concerned is now moot and your correction is 18 months too late.
On a personal note it is IMO very poor form to go round on an amateur chemistry forum brandishing your sois-dissant docrorate like a club with wish to
bash all lesser chemists. There are many Ph.D. chemists on this forum, and I have not seen any of them being so crass as to establish an elite class.
So, are you done, or do you have anything else to add about red mercury, old posts, or the price of tea in China? Because I for one would prefer to
return to the thread topic.
[Edited on 4-7-2008 by Sauron]
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