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Sauron
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No problem, just underscoring.
The following is reference 6 from the first Hoffmann paper above. It is a 1939 JACS paper describing the mechanism and practical aspects of the
"redistribution reaction" and is necessary to fully comprehend Hoffmann's papers dealing with transesterification and redistribution prediction and
control.
Incidentally I searched for Sigmund Eckhaus in the author field of ACS Publications search engine and found only a single entry in Ind.Eng.Chem
dealing with paint filters. Not sure if same man or no.
My working hypothesis is that Friedrich W.Hoffmann was principle scientist on this project at Edgewood, while Eckhaus may be a chemical engineer
involved in the process development (industrialization) rather than the basic chemistry and bench scale research. No denigration is intended; both
are vital. But I am more interested in the chemistry and much less so in the scaleup and technology.
The following link is to a forum thread, the last three posts at bottom of page contain attachments of one US and two GB (UK) patents on VX. I posted
these in December 2006.
The US Patent 3,911,059 dated 1975 is to Eckhaus, Davis, Moore (Thomas L.Moore, frequent collaborator with Hoffmann). One of Hoffmann's patents is
cited as prior art and his papers on transesterification are cited in the patent text. One of the UK patents, q.v. is also cited.
We know that much of the actual work on VX in UK and US was done in the early 50s, but not allowed to be published, or secrecy orderes lifted on
patents till very late 50s or later.
So note that 1973 represents a quarter of a century later date than the original work and, I would guess, this invention consists of improvements to
the process. Most likely improvements made during the 1960s.
[Edited on 23-6-2008 by Sauron]
[Edited on 23-6-2008 by Sauron]
Attachment: redistribution.pdf (746kB)
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Sauron
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Ritter,
What have you in that large patent collection or the 2006 book regarding preparation of the di-isopropyl-2-aminoethanol
And did you get my PMs regarding 4shared, Kosolapoff etc?
The Schrader articles are in German, from Angew.Chemie. I have them on a CD and will dig them out.
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Ritter
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| Quote: | Originally posted by Sauron
Ritter,
What have you in that large patent collection or the 2006 book regarding preparation of the di-isopropyl-2-aminoethanol
And did you get my PMs regarding 4shared, Kosolapoff etc?
The Schrader articles are in German, from Angew.Chemie. I have them on a CD and will dig them out. |
Many thanks!
Ritter
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Ritter
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| Quote: | Originally posted by Sauron
Schrader's paper from Angew Chem (in German)
[Edited on 23-6-2008 by Sauron] |
I downloaded the file but Adobe Acrobat sent an error message that the file was damaged & could not be repaired. Could you check it on your end
& then try posting it again?
Danke sehr!
Ritter
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Sauron
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My copy is fine.
The forum must have messed it up, perhaps due to size.
Let me consider what to do about this.
I split the pdf into two parts.
Let's see if this works.
Here's first half.
[Edited on 24-6-2008 by Sauron]
Attachment: Pages from Schrader Prt 1.pdf (1MB)
This file has been downloaded 1590 times
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Sauron
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That works. I downloaded it to check.
So here's other half.
This one also downloaded OK.
If you have Adobe Acrobat Pro you can reassemble them into single pdf. That's what I used to break it in two.
You never did answer my question, Ritter, about lit. on preparation of N,N-di-isopropyl-2-aminoethanol.
[Edited on 24-6-2008 by Sauron]
Attachment: Pages from Schrader Prt 2.pdf (1.1MB)
This file has been downloaded 964 times
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Sauron
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Just as an addendum to the earlier discussion upthread, as I am no longer able to edit those posts, the VX process as described was incomplete because
it proceededmonly so far as the thionation of QL (the transester). The final step in the prep of VX is the thermal isomerization of the resulting
thiolated transester
MeP(=S)(OEt)(OCH2CH2N(Pri)2
to
MeP(=O)(OEt)(SCH2CH2N(Pri)2
Now if you go back and look at Amiton (code VG) you will see that it is in fact not precisely an analog:
(EtO)2P(=S)SCH2CH2N(Et)2
and thus is derived from phosphorus sulfochloride PSCl3 the sulfur analog of POCl3.
So seven variations into the original ICI insecticidal study, they were still looking at relatives of Parathion and Malathion (q.v.) and had not yet
started alkylating the phosphorus atom.
Once they did, they were of course paralleling part of the G-agent series
RP(=O)(OR1)-X
So once they were onto
RP(=O)(OR1)S-CH2CH2-N(R2)2
the pertinent structural elements were three.
Alkyl ligand R linked to P
O-ester R1
Alkyl substituents R2 at N
A lot of further clues can be garnered from studying F.W.Hoffman's many papers in JACS and JOC.
The thermal isomerization of the alkylthiophosphonate O-esters to alkylphosphonate S-esters was first noticed during attempts to distill the former.
Partial isomerization resulted, and the isomerized product was found to be several orders of magnitude more toxic than the already very toxic
O-isomer. Similar phenomena were encountered with related insecticides such as Systox and Parathion.
Apart from its exploitation in the Eckhaus et al-patented production process this is also the basis of the binary VX2 system, in which the transester
QL is mixed with rhombic sulfur or dimethyl polysulfide in the (cancelled) 8-inch artillery shell program.
A VX like analog of Amiton would be
EtP(=O)(OEt)SCH2CH2NEt2
which is probably part of the series but I don't know the code name.
[Edited on 25-6-2008 by Sauron]
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Ritter
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| Quote: | Originally posted by Sauron
That works. I downloaded it to check.
So here's other half.
This one also downloaded OK.
If you have Adobe Acrobat Pro you can reassemble them into single pdf. That's what I used to break it in two.
You never did answer my question, Ritter, about lit. on preparation of N,N-di-isopropyl-2-aminoethanol.
[Edited on 24-6-2008 by Sauron] |
Thanks for the downloads.
I checked on this yesterday & found nothing. I could guess at some prep methods. Forming the aklali metal salt of the amine with BuLi followed by
addition of the chlorohydrin would be one. In situ formation of ethylene oxide by treating the chlorohydrin with 3 eq. of 2M NaOH at RT would
be another. I think ethylene oxide is likely your best bet.
Ritter
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Ritter
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| Quote: | Originally posted by Sauron
Just as an addendum to the earlier discussion upthread, as I am no longer able to edit those posts, the VX process as described was incomplete because
it proceeded only so far as the thionation of QL (the transester). The final step in the prep of VX is the thermal isomerization of the resulting
thiolated transester |
I thought the thionation/thermal isomerization occurred spontaneously. This was the basis for both the final manufacturing process & the binary
shells/bombs.
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Sauron
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Eckhaus describes two discrete steps for these in his patent.
First the thiation, and then the isomerization. The addition of sulfur to the OP is almost always exothermic and usually done with external cooling.
The isomerization time depends on temperature used, Eckhaus et al recommend higher temperatures and shorter rxn times.
How that relates to the binary, deponent knoweth not.
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Ritter
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| Quote: | Originally posted by Sauron
Eckhaus describes two discrete steps for these in his patent.
First the thiation, and then the isomerization. The addition of sulfur to the OP is almost always exothermic and usually done with external cooling.
The isomerization time depends on temperature used, Eckhaus et al recommend higher temperatures and shorter rxn times.
How that relates to the binary, deponent knoweth not. |
I'll have to read Eckhaus more closely. I believe you can isolate the P=S intermediate but the whole point of the binary munitions was to use the heat
of the reaction with S8 or CH3SSSSCH3 to accomplish the isomerization at the same time, in a matter of seconds.
In FM 3-11.9 they state (p. 11-71): 'Reacts with sulfur and sulfur compounds to produce VX or VX-like compounds.' footnoted as being from Nowlin, T.E.
et al A New Binary VX Reaction-Two-Liquid System (U), EATR 4700, USA Munitions Command, Edgewood Arsenal, MD, November 1972. UNCLASSIFIED
Report (AD524088). It also states that, not surprisingly, that QL reacts with selenium & selenium compounds. Since Se is just below S in the
Periodic Table, seleno-VX would be the likely result.
Under QL toxicity, they give no data.
Ritter
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| Quote: | Originally posted by Sauron
Eckhaus describes two discrete steps for these in his patent.
First the thiation, and then the isomerization. The addition of sulfur to the OP is almost always exothermic and usually done with external cooling.
The isomerization time depends on temperature used, Eckhaus et al recommend higher temperatures and shorter rxn times.
How that relates to the binary, deponent knoweth not. |
I just read his patent & while Eckhaus claims the P=S & P=O compounds as discrete compounds, he did not isolate & characterize the P=S
compound but instead kept it from isomerizing by using a DryIce/glycol bath to remove the heat formed in this very exothermic reaction. He then
heated it to accomplish the isomerization in a second step.
The great amount of effort that Edgewood went to in developing the binary VX weapons was actually spearheaded in part by Eckhaus. From War of
Nerves, p. 161:
| Quote: | | Given the lack of institutional support [by the U.S. Army's Chemical Corps] for binary weapons, Sigmund Eckhaus, the director of the VX pilot plant,
had to "smuggle" samples of QL to the binary development team. |
p. 160:
| Quote: | | Building on [Friedrich] Hoffmann's work...[ Edgewood] developed a concept for a binary VX bomb in which powdered sulfur would be injected into a
liquid solution of QL. |
In the binary weapons the heat of the sulfurization reaction also drove the P=S compound to isomerize immediately as it was formed to the P=O VX.
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Sigmund Eckhaus is apparently still with us. His name is in the list of donors on the AIChE's web site: http://www.aiche.org/About/Foundation/CentennialCelebrationA.... Tucker footnotes having interviewed him for his 2006 book.
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Sauron
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I did not get the notion from the Eckhaus patent, that the penultimate step (addn of S or Me2Sn to the QL, wis sufficiently exothermic to accomplish
the isomerization in seconds. I would think that there is enough information in the literature (of P and S chemistry in general) to come up with an
educated guess as to how many kcal or whatever units, we are talking about. Eckhaus gave a few examples of the time/temperature dependency in the
patent, we can extrapolate from that.
There is certainly the possibility to consider that the rxn exotherm was assisted by external heating and/or that the kinetics were accelerated by
catalysis, why not?
However, we are starting to cross the line from chemistry to something less welcome on this forum.
The transester QL was/is certainly quite toxic in its own right, just not so relative to VX proper. Arguendo, the binary designers may have settled
for a mixture, incomplete isomerization, unlike the more leisurely isomerization (minutes) that could be induldged at the pilot plant.
I have obtained all six papers in the "Organic Phosphorus Compounds" series by F.W.Hoffmann et al in JACS. I compiled them into a single pdf of 3.5 Mb
too large to post here but I can place it in my 4shared folder if you or other members would like to read it.
Part 1 concerns the preparation and use of the MeCl-PCl3-AlCl3 complex and its conversion to alkylphosphonate dichlorides,diesters or monoester
chloridates. This is an extension of the seminal work of J.P.Clay in late 1940s, see attached from JOC.
As described upthread, reduction of same complex by various means, but most conveniently using PhPCl2 and POCl3, gives MePCl2.
Papers II through V describe in detail the preparation of various inorganic and OP esters and sulfur analogs and their transesterification.
Paper VI, structure-activity relationships versus AChE inibition.
Paper IV has already been posted, it was the one describing the diester.
I think you will find these well worth your time and attention.
[Edited on 26-6-2008 by Sauron]
Attachment: jo01146a010.pdf (228kB)
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Sauron
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PS Michael Crichton's work of fiction "Binary" is said to have badly rattled the Soviets. It has been cited as part of the rationale for their
novichok program, although this strikes me as absurd on its face.
Why should binary VX be more intimidating than normal VX?
And the advantages of the Russian 3rd/4th/5th generation CW programs need no further justification. They positioned themselves for a treaty breakout
before ever signing the (CWC) treaty. A de facto breach, certainly even if one accepts the rather thin de jure arguments that these compounds are not
coverered by treaty.
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Ritter
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| Quote: | | Quote: | Originally posted by Sauron
I did not get the notion from the Eckhaus patent, that the penultimate step (addn of S or Me2Sn to the QL, wis sufficiently exothermic to accomplish
the isomerization in seconds. |
On the other hand, I did. This fact is the essence of the binary system: you need the heat generated by rxn #1 to drive rxn #2 while the weapon is in
flight = seconds.
| Quote: | | The transester QL was/is certainly quite toxic in its own right, just not so relative to VX proper. Arguendo, the binary designers may have settled
for a mixture, incomplete isomerization, unlike the more leisurely isomerization (minutes) that could be induldged at the pilot plant.
|
The Tucker book remarks that the CW Service was against binary VX because a weapon would not deliver 100% VX.
| Quote: | I have obtained all six papers in the "Organic Phosphorus Compounds" series by F.W.Hoffmann et al in JACS. I compiled them into a single pdf of 3.5 Mb
too large to post here but I can place it in my 4shared folder if you or other members would like to read it.
Part 1 concerns the preparation and use of the MeCl-PCl3-AlCl3 complex and its conversion to alkylphosphonate dichlorides,diesters or monoester
chloridates. This is an extension of the seminal work of J.P.Clay in late 1940s, see attached from JOC.
As described upthread, reduction of same complex by various means, but most conveniently using PhPCl2 and POCl3, gives MePCl2.
Papers II through V describe in detail the preparation of various inorganic and OP esters and sulfur analogs and their transesterification.
Paper VI, structure-activity relationships versus AChE inibition.
Paper IV has already been posted, it was the one describing the diester. |
I went to your 4shared folder & could not find the pdfs. Please give me a URL or some more info. Thanks!
|
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Sauron
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The pdf was uploadubg, now completed.
http://www.4shared.com/dir/2245331/5a78115f/sharing.html
No, I understand completely that the rxn time would have to be in (few) seconds, I just did not get any sense from the Eckhaus patent that such short
time was feasible with procedure as described. The inventors described examples of isomerizations complete (substantially) in minutes. The
temperatures IIRC were in the 100-200 C range. I see the need for much faster times, I just don't see the exotherm producing all that is required.
Hence my speculations regarding auxiliary heating and/or some sort of kinetic manipulation (catalysis).
I admit I have not paid much attention to this, but, attention can be paid and I don't see anything occult about the thermodynamics. A little time
with a MO package would certainly tell the tale.
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Ritter
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| Quote: | Originally posted by Sauron
No, I understand completely that the rxn time would have to be in (few) seconds, I just did not get any sense from the Eckhaus patent that such short
time was feasible with procedure as described. |
They had to cool rxn #1 with a Dry Ice/glycol bath in order to prevent rxn#2 from taking place as soon as the P=S intermediate was formed. I
do not know if the isomerization (rxm #2) is exothermic or not but the need for Dry Ice/glycol indicates some serious exothermy in rxn #1.
As Tucker had interviewed Eckhaus, I would believe what is in his book.
p. 179:
| Quote: | [They] had used a propellant to fire a few grams of particulate sulfur directly into the QL solution, triggering the spontaneous chemical reaction
that yielded VX. .....
The reaction worked perfectly, going to completion in about five seconds and generating VX and a great deal of heat.
|
[Edited on 25-6-2008 by Ritter]
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Sauron
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QL solution?
So the QL had to be solvated rather than reacting neat with sulfur?
This may explain the Army's objection, as any solvent would reduce the payload deliverable in a munition of a given size compared to a munition loaded
with pure agent.
Anyway, it is not my intention to wax argumentative about the pros and cons of VX2. The chemistry is the same, and it's the chemistry that interests.
-----------------------------
Eckhaus' patent lawyer ought to be flogged or at least take a refresher course in something.
The patent example describes 3221 g of the transester as 1.37 moles.
And 425 g sulfur as 1.36 moles.
I submit that these are off by a factor of 10. And I may be nitpicking but that's gram-atoms of sulfur not moles.
13.7 moles of QL and 13.6 g-atoms S. It is obvious from the 4 liter flask that these amounts are correct.
Also it is clear that solvent is not required.
[Edited on 26-6-2008 by Sauron]
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Ritter
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| Quote: | Originally posted by Sauron
QL solution?
So the QL had to be solvated rather than reacting neat with sulfur?
This may explain the Army's objection, as any solvent would reduce the payload deliverable in a munition of a given size compared to a munition loaded
with pure agent. |
That and their objection to the reaction (at least in the early stages of its development) not going entirely to completion before impact.
| Quote: | Anyway, it is not my intention to wax argumentative about the pros and cons of VX2. The chemistry is the same, and it's the chemistry that interests.
-----------------------------
Eckhaus' patent lawyer ought to be flogged or at least take a refresher course in something.
The patent example describes 3221 g of the transester as 1.37 moles.
And 425 g sulfur as 1.36 moles.
I submit that these are off by a factor of 10. And I may be nitpicking but that's gram-atoms of sulfur not moles.
13.7 moles of QL and 13.6 g-atoms S. It is obvious from the 4 liter flask that these amounts are correct.
Also it is clear that solvent is not required
[Edited on 26-6-2008 by Sauron] |
There is also a very important detail about this system that's disclosed in the patent that I will not post here so that I'm not writing a VX
"cookbook."
Ritter
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| Quote: | Originally posted by Sauron
QL solution?
So the QL had to be solvated rather than reacting neat with sulfur?
This may explain the Army's objection, as any solvent would reduce the payload deliverable in a munition of a given size compared to a munition loaded
with pure agent. |
That and their objection to the reaction (at least in the early stages of its development) not going entirely to completion before impact.
| Quote: | Anyway, it is not my intention to wax argumentative about the pros and cons of VX2. The chemistry is the same, and it's the chemistry that interests.
-----------------------------
Eckhaus' patent lawyer ought to be flogged or at least take a refresher course in something.
The patent example describes 3221 g of the transester as 1.37 moles.
And 425 g sulfur as 1.36 moles.
I submit that these are off by a factor of 10. And I may be nitpicking but that's gram-atoms of sulfur not moles.
13.7 moles of QL and 13.6 g-atoms S. It is obvious from the 4 liter flask that these amounts are correct.
Also it is clear that solvent is not required
[Edited on 26-6-2008 by Sauron] |
There is also a very important detail about this system that's disclosed in the patent that I will not post here so that I'm not writing a VX
"cookbook."
Ritter
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I reread the sulfurization/isomerization procedure description and you are correct that a solvent was not used, at least in this lab work.
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Sauron
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There are any number of possible such points. However there is little danger in writing a "VX cookbook" as wannabe cooks will be dead faster than one
can say acetylcholinesterase. No need to be coy. I've been looking at that patent since the early 1980s.
In one of Hoffmann's six part JACS series of papers, he describes a sulfurization reaction that was conducted in a solvent, employed a small amount of
suspended AlCl3 and used a 100% excess of sulfur, the last two points being contrary to the teachings of the Eckhaus (et al) patent, which specifies a
slight deficiency of sulfur (slight excess of QL) and makes no mention of any third substance. I mention this only to show that the sulfurization of
phosphorus (III) compounds occurs in conditions not so narrow as the patent.
MePCl2 (and other alkyl or aryl dichlorophosphines) can be sulfurized to MeP(=S)Cl2. The half ester MeP(OEt)Cl and the diester MeP(OEt)2 can be
sulfurized. All these reactions are highly exothermic. I don't think it is necessary to explain why doing so is not practical compared to waiting till
after the transesterification, because the reason is obvious to anyone who has read and understood the literature. The sulfurization procedures are
identical to those described by Eckhaus, or their variants as in Hoffmann. I am rather desultorily rereading Kosolapoff hoping to find how far back
this reaction was known.
Thiation bu exchange of S for O was known as long ago as the mid 19th century using P2S5, examples can be found in Org.Syn. The desulfurization of
resulting compounds to the alkyldichlorophospite using PhPCl2 is a much more contemporary discovery. In this fashion MeP(=O)Cl2 ->MeP(=S)Cl2 -.
MePCl2. Maybe not the best way but there it is.
As you can see from the UK patents the ICI folks and their MOD counterparts had their own ideas about preparing VX; however they never got around to
process engineering of it, did they? (Or any of the earlier V-agents save only Amiton, the illfated commercial application.)
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Ritter
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I have a strong hunch that if you dig around the Internet long enough you can find almost any bit of info.
This military publication, Guide to Scheduled Chemicals, (see http://dtirp.dtra.mil/products/products/129p.htm contains a wealth of info, including this gem:
| Quote: | Diethyl methylphosphonite
Synonym: TR O,O-Diethyl ester of methlphosphonus acid
Schedule: 2B
CAS No: 15715-41-0
Synthesis: : Methylphosphonus dichloride and ethanol
Catalyst: : Ammonia
Use: Scheduled precursor to QL
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Since this is from an official source, I think I've answered my original question at the top of this thread: the code for 'diester' appears likely to
be TR.
And from the same page, and in keeping with the military's penchant for assigning code names to substances used in classified projects, we find a
second gem:
| Quote: | Chemical: KB
See: N,N-Diisopropyl-(beta)-aminoethanol
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Also from the same page is this code for a by-product of the transester process:
| Quote: | LT
See: Bis(2-diisopropylaminoethyl) methylphosphonite |
and even more:
| Quote: | Chemical: Methylphosphonothioic dichloride
Synonym: SWS Dichloromethylphosphine Phosphonothiotic dichloride, methyl
Schedule: 2B
CAS No: 676-98-2
Use: Scheduled precursor to YLS and VX
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But wait, there is more on this:
| Quote: | Chemical: O,O-Diethyl methylphosphonothionate
Synonym: TRS Diethyl methylphosphonothionate Methylphosphonothioic acid, O,O-diethyl ester
Schedule: 2B
CAS No: 6996-81-2
Use: Scheduled precursor to YLS
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and still more:
| Quote: | Chemical: O-Ethyl methylphosphonothiolic acid
Synonym: YLS Ethyl ThioMPA O-Ethyl methylphosphonothioic acid Methylphosphonothioic acid, O-ethyl-ester
Schedule: 2B
CAS No: 18005-40-8
Use: Scheduled precursor to VX; degradation product of VX (hydrolysis)
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and yet more:
| Quote: | Chemical: O-Ethyl methyl phosphinic acid
Synonym: Ethyl methylphosphinate YL Ethoxymethylphosphine oxide
Schedule: 2B
CAS No: 16391-07-4
Use: Scheduled precursor to VX; degradation product of QL (hydrolysis)
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and more:
| Quote: | Chemical: O-Ethyl O-2- diisopropylaminoethyl methylphosphonothionate
Synonym: CV O-Ethyl O-2-diisopropylaminoethyl methylphosphonothiolate phosphonothioic acid, methyl-, O- (2-diisopropylaminoethyl)
O-ethyl ester
Schedule: 2B
CAS No: 71840-25-0
Use: Scheduled precursor to VX
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CV is the reaction product of QL with sulfur. It rearranges under heating to give VX.
So the synthesis of VX as worked out at Edgewood is SW > TR, TR + KB > QL + LT, QL + NM or NE > CV > VX.
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Ritter
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\"The production of too many useful things results in too many useless people.\"
Karl Marx
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Ritter
Hazard to Others
Posts: 370
Registered: 20-6-2008
Location: Earth
Member Is Offline
Mood: Curious
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From that same list of precursor chemicals, I found this:
| Quote: | Chemical: Diethylphosphorachloridite
Synonym: DEPCI Phosphorochloridous acid, diethyl ester Diethyl chlorophosphite Ethyl phosphorochloridite
CAS No: 589-57-1
Use: Unscheduled precursor to Tabun
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This is the product I posted on the 21st as being a precursor for 'diester' via Grignard reaction in a Hoechst AG patent. While they list it as being
a Tabun precursor, we know it can also be a VX precursor.
Ritter
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\"The production of too many useful things results in too many useless people.\"
Karl Marx
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