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Sauron
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One is the half ester, an undesirable byproduct of the reaction of SW with ethanol in presence of a tertiary base.
The other is the diester, the main and desired product of that esterification.
The tertiary amine of choice is diethylaniline.
Methylphosphinous acid, MeP(OH)2 is another possible byproduct and degradation product, although I would expect it to rapidly oxidize to
methylphosphonic acid MeP(=O)(OH)2 in the environment Also a degradation product of GB and GD and most G-agents save GA.
Another is the O-ethyl chloridate, MeP(OEt)Cl. Product of incomplete esterification of SW but wothout hydrolysis of the remaining chlorine to the
acid.
In the case of MeP(OEt)OH or MeP(OH)Cl, the possibility exists for tautomerism between these tervalent structures and the pentavalent MeP(=O)(OEt)H
and MeP(=O)(Cl)H which would also be undesirable.
Review the similar relationship bvetween trialkyl phosphites, dialkyl hydrogen phosphites, and dialkyl phosphates. See Saunders for how this
underirable byproduct turned out to be useful. Treatment of the dialkyl hydrogen phosphite with N-chlorosuccinimide produced the
dialkylphosphorochloridate, readily reacted with alcohol to get back to the trialkyl phosphite.
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Ritter
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I'm pleased that I was able to run down & identify the code names for all the Edgewood VX starting materials & process intermediates.
Apparently there are several routes to make VX. Have we covered EMPTA (O-ethyl methylphosphonothioic acid)? This is said to be either an intermediate
or a hydrolysis product of the Iraqi VX process, though I thought they only had sarin & perhaps another G-agent only. It is the P=S isomer of YLS.
Another precursor is S-(2-diisopropylaminoethyl)methyl-phosphonthioic acid described in USH346 by Edgewood. See also US3903210 by them.
It is interesting to note that that chemical precursor schedule does not list methylphosphonothioic O,O-acid, one of the intermediates described in
the patent.
| Quote: | Chemical: S-2-Diisopropylaminoethyl methylphosphonothioic (acid)
Synonym: S-2-(Diisopropylamino) ethyl methylphosphonothioic EA 2192 Phosphonothioic methyl
Schedule: 2B
CAS No: 73207-98-4
Use: Scheduled precursor degradation product of VX (hydrolysis)
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[Edited on 26-6-2008 by Ritter]
[Edited on 26-6-2008 by Ritter]
[Edited on 26-6-2008 by Ritter]
[Edited on 26-6-2008 by Ritter]
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Ritter
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Gerhard Schrader did some work on V-agent-like insecticides while at Bayer. See US2918488 (1959) at http://tinyurl.com/6l6f39
.
[Edited on 26-6-2008 by Ritter]
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Sauron
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It seems like that military document is not always accurate, or was written and edited by non-chemists. Obviously that last acid you mentioned is a VX
degredation product and has nothing to do with G-agent.s
As to the code designations, it raises more questions than it answers. Suddenly we have three-letter rather than two-letter codes to content with, and
then there are the V-numeric codes.
At least in the latter case we can take a stab at an explanation.
I would guess that the code list starts at VA, we know Amiton is VG and that is still an early, non-alkylated (no C-P) structure. VX is pretty late in
the series. Whewn they got to VZ they started into V1, V2 etc as an extension. Just surmise, but reasonable and it will have to do till harder intel
comes along.
Anyway attaboy!
Part of the inherent wekness of CWC is that is is limited to past agents and past methods and precursors. Thus it has institutional blinders. It
really is focused on large industrial production, and logistics.
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| Quote: | Originally posted by Sauron
It seems like that military document is not always accurate, or was written and edited by non-chemists. Obviously that last acid you mentioned is a VX
degredation product and has nothing to do with G-agent.s |
If you read USH436, it describes this acid as a cholinesterase inhibitor, not a hydrolysis product. Apparently there were several routes to make VX.
What about EMPTA?
| Quote: | As to the code designations, it raises more questions than it answers. Suddenly we have three-letter rather than two-letter codes to content with, and
then there are the V-numeric codes.
At least in the latter case we can take a stab at an explanation.
I would guess that the code list starts at VA, we know Amiton is VG and that is still an early, non-alkylated (no C-P) structure. VX is pretty late in
the series. Whewn they got to VZ they started into V1, V2 etc as an extension. Just surmise, but reasonable and it will have to do till harder intel
comes along.
Anyway attaboy! |
Thanks. It was a rewarding experience. Thanks for the collaboration.
Ritter
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Sauron
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With regard to the US patent (US5128495).
It is not necessary to treat diethyl hydrogen phosphite with two mols PCl3 in presence of the (very nasty) HMPA in order to obtain the diethyl
chlorophosphite. The British (Saunders, Gerrard) found that NCS (N-chlorosuccinimide perferms this transformation. This was discovered in late
30s-early 40s and not published till postwar in J.Chem.Soc. and later referenced in Saunders book (q.v., in forum library.
This was an important breakthrough in the DFP program because they were reacting PCl3 with alcohols to obtain trialkyl phosphites, a reaction that
required large amounts of costly pyridine. Without the tertiary base the main product was diethyl hydrogen phosphite (of whatever dialkyl hydrogen
phosphite concerned.) So the observation that the P-H could be replaced by P-Cl via NCS was significant; the resulting compound could then be
fluoridated directly to DFP pr another investigational dialkyl fluorophosphate.
Anyway, the patent illustrates a route to MePCl2 via Grignard for sure.
However, GA is a simpler matter. There the starting material is POCl3, rather ubiquitous and easy to make. The only other materials required are
dimethylamine (readily made from DMF), ethanol and NaCN or KCN.
Usually, diethylamine is reacted with POCl3 in presence of equimolar pyridine or diethylaniline to make the dimethylphosphoroamidic dichloride. This
is then reacted with a saturated ethanolic solution of NaCN to effect both the other additions at same time.
Variations of this are of course possible, but there is no need at all to get elaborate and expensive with a tervalent phosphorus reagent, so I think
the staement that the diethyl hydrogen phosphite is a GA precursor, is an error in that military manual.
[Edited on 27-6-2008 by Sauron]
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I have been reading that document and I must say it is poorly organized and a pain to wade through. However it is certainly profitable from th
standpoint of identifying some agents not previously mentioned or described in the open literature, and will doubtless precipitate a flurry of new
editions of the various CW encyclopeadias, good, bad, and ugly.
There are a number of alternative synthetic routes of entry to VS precursors mentioned in there; I will cite just one or two for example. The reaction
of methane with PF3 (both gaseous) to produce MePF2. Somewhat more practically, the reaction of PCl3 with MeI and sodium metal to produce MePCl2.
Obviously MeCl and MeBr would react similarly.
The manual is on shaky ground in spots. It mentions the complex of AlCl3 and PCl3 as the Perrin-Kinnear complex, but fails to mention any alkyl halide
which is an essential component, and insists that methylene chloride is a catalytic solvent for the complex formation. Perrin and Kinnear did describe
the complex in J.Chem.Soc., but were not first to do so, the honor goes to J.P.Clay in JACS whom they cited. F.W.Hoffmann et al demonstrated in JACS
that methylene chloride was not required; the complex forms without solvent in at least some cases, including the important one of [MePCl3][AlCl4].
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http://dtirp.dtra.mil/products/products/129p.htm | Quote: |
======================================
Chemical: (N,N-Dimethylamino) ethyl chloride hydrochloride Synonym: 2-Dimethylaminic ethyl chloride hydrochloride Dimethylaminoethyl chloride
hydrochloride
Schedule: 2B
CAS No: 4584-46-7
Use: Scheduled precursor to V1
==================================
Chemical: (N,N-Dipropylamino) ethyl chloride hydrochloride
Synonym: 1-Propanamine, N-(2- chloroethyl)-N-propyl-hydrochloride N-(2-Chloroethyl)-N-Propyl-1- propanamine hydrochloride
(2-Chloro-ethyl)-dipropyl-amine hydrochloride
Schedule: 2B
CAS No: 4535-86-8
Use: Scheduled precursor to V2
====================================
Chemical: 2-(N,N-Diisopropylamino) ethyl chloride hydrochloride
Synonym: (2-Chloroethyl) diisopropylamine hydrochloride (.beta.-chloroethyl)diisopropylamine hydrochloride
Schedule: 2B
CAS No: 4261-68-1
Use: Scheduled precursor to VX, VS, V4, and V5 ==================================
N,N-Diisopropyl- (beta)-aminoethanol
Synonym: KB Ethanol, 2-(bis(1- methylethyl)amino) 2-(Bis(1-methylethyl) amino) ethanol (N,N-Diisopropylamino) ethanol
Schedule: 2B
CAS No: 96-80-0
Use: Scheduled precursor to QL, VX, VS, V4, and V5 ======================================
This is the first time I've seen V-agents listed with V# designations instead of V-letter codes.
[Edited on 27-6-2008 by Ritter] |
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| Quote: | Originally posted by Sauron
With regard to the US patent (US5128495).
It is not necessary to treat diethyl hydrogen phosphite with two mols PCl3 in presence of the (very nasty) HMPA in order to obtain the diethyl
chlorophosphite. The British (Saunders, Gerrard) found that NCS (N-chlorosuccinimide perferms this transformation. This was discovered in late
30s-early 40s and not published till postwar in J.Chem.Soc. and later referenced in Saunders book (q.v., in forum library). |
They used triethyl phosphite in that patent. Do you have a pdf of that JCS article?
| Quote: | This was an important breakthrough in the DFP program because they were reacting PCl3 with alcohols to obtain trialkyl phosphites, a reaction that
required large amounts of costly pyridine. Without the tertiary base the main product was diethyl hydrogen phosphite (of whatever dialkyl hydrogen
phosphite concerned.) So the observation that the P-H could be replaced by P-Cl via NCS was significant; the resulting compound could then be
fluorinated directly to DFP pr another investigational dialkyl fluorophosphate.
Anyway, the patent illustrates a route to MePCl2 via Grignard for sure.[ |
Don't you mean MeP(OEt)2?
| Quote: | However, GA is a simpler matter. There the starting material is POCl3, rather ubiquitous and easy to make. The only other materials required are
dimethylamine (readily made from DMF), ethanol and NaCN or KCN.
Usually, diethylamine is reacted with POCl3 in presence of equimolar pyridine or diethylaniline to make the dimethylphosphoroamidic dichloride. This
is then reacted with a saturated ethanolic solution of NaCN to effect both the other additions at same time.
Variations of this are of course possible, but there is no need at all to get elaborate and expensive with a tervalent phosphorus reagent, so I think
the staement that the diethyl hydrogen phosphite is a GA precursor, is an error in that military manual.
[Edited on 27-6-2008 by Sauron] |
From Tucker, p. 111:
| Quote: | | ....Edgewood....also worked on an industrial manufacturing process for Sarin [GB]. After failing to develop a simplified 4-step method, they decided
to adopt the German 5-step approach known as the DMHP (dimethyl hydrogen phosphite) process. |
So this may be
an error in the military manual, as they go on to say that thev DMHP (or DEHP) process involves use of anhydrous HF, wehich is not involved with GA
chemistry.
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Sauron
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No, not MeP(OEt)2.
The Brits (late 30s-early to mid 40s) were focused on dialkyl fluorophosphates, particularly DFP, diisopropyl fluorophospate, or what we now call
phosphonofluoridate.
(PriO)2POF
These compounds are about as toxic as HCN and much less so than G agents; however they are AChE inhibitors and played an important role in development
of future insecticides and OP military agents. There is no C-P bond. See Saunders' book.
Saunders also benefitted from British intelligence of Schrader's work and prepared tabun and sarin in his lab very early on by routes differing from
Schrader's own. (Soman of course did not come into the picture till a few years later.)
The significance of dialkyl hydrogen phosphites in G-agent production is related to the role of these compounds in the Michaelic-Arbusov reaction. In
this reaction an alkyl halide such as MeI is reacted with a trialkyl phosphite such as tri-isopropyl phosphite under suitable conditions and
alkylation and rearrangement occurs. The product is MeP(=O)(OPri)2
In a modification of this reaction the di-dsopropyl hydrogen phosphite can be used instead.
The alkylphosphonic diester can be exploited in several different ways to end up with G-agents such as GB, GD, GE, GF etc.
One or both alkoxy groups can be replaced by chlorine.
If both alkoxy groups are replaced a different alcohol can be reacted with the alkylphosphonic dichloride to obtain the desired
alkylphosphonochloridate ester.
The final step is to replace the Cl with F.
Alternatively if the alkoxy group already present is the desired one then only one is replaced with chlorine, and then exchanged for fluorine.
On the industrial scale the usual chlorinating agent is phosgene and the usual fluorinating agent is anhydrous HF but of course there are other
choices.
The Germans had a lot of problems handling fluorine and neat HF but for obvious reasons having to do with Dupont and the UF6 diffusion process, the US
did not.
The process engineering of G-agents is beyond my ken, as I am not a CE. On the bench scale there are many options, again we are constrained by our old
friends fear and common sense from going beyond doodling on paper.
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Ritter
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| Quote: | Originally posted by Sauron
No, not MeP(OEt)2.
|
That Hoechst patent that you reference has to do with converting trialkyl phosphites with PCl3 & hexamethylphosphoramide into chlorophosphites
which are then converted to alkyl phosphite esters (such as MeP(OEt)2)via coupling with alkyl Grignard reagent. It has nothing to do with
alkyl(chloro)phosphines.
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Sauron
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My point was that if you want dialkyl chlorophosphites you do not need to jump through all those hoops.
If you react PCl3 with an alcohol (three moles) in absence of tertiary base you get c.80% yield of the (RO)2P-OH which is tautomer of (RO)2P(=O)-H and
that is the dialkyl hydrogen phosphite. Now treating with Cl2, on a large scale, or NCS on a bench scale gets you the (RO)2P(=O)Cl. Again high yield.
I'll have to read the patent but it sounds like a more complex answer to a simple problem.
The military manual implied that the alkylation of the product of this gave SW not DC, unless I read it wrong. DC is not a V agent precursor, but a G
agent one.
[The reason that in the reaction of PCl3 with alcohol, in absence of tertiary base like pyridine, the HCl formed cleaves the labile third alkoxy
group, producing alkyl chloride and the dialkyl hydrogen phosphite.
The situation is much worse with PBr3. In that case you get a mixture of alkyl dihydrogen phosphite, dialkyl hydrogen phosphite and phosphorous acid,
along with lots of alkyl bromide. This is why the conventional wisom is that PBr3 is good for making alkyl bromides and useless for making trialkyl
phosphites. The conventional wisdom is not quite right, as it turns out. But there we are.
[Edited on 28-6-2008 by Sauron]
Attachment: Pages from phosphorus_fluorine_toxicity.pdf (190kB)
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| Quote: | Originally posted by Sauron
My point was that if you want dialkyl chlorophosphites you do not need to jump through all those hoops.
If you react PCl3 with an alcohol (three moles) in absence of tertiary base you get c.80% yield of the (RO)2P-OH which is tautomer of (RO)2P(=O)-H and
that is the dialkyl hydrogen phosphite. Now treating with Cl2, on a large scale, or NCS on a bench scale gets you the (RO)2P(=O)Cl. Again high yield.
|
The P=O compound you show is a phosphonate, not a phosphonite. The compound desired is (RO)2PCl. As far as I know there are only 2 known ways to get
it: one, reaction of SW with EtOH in the presence of organic base, or two, by alkyl Grignard replacement of the chlorine in (RO)2PCl. Since SW is
difficult to make and I believe pyrophoric in air, the second (Hoechst) approach seems more attractive.
| Quote: | | I'll have to read the patent but it sounds like a more complex answer to a simple problem. |
Please.
| Quote: | | The military manual implied that the alkylation of the product of this gave SW not DC, unless I read it wrong. DC is not a V agent precursor, but a G
agent one. |
SW is methyl(dichloro)phosphine, made from MeCl & PCl3. It is the Edgewood starting point for VX. DC (dichlor) is a G-agent precursor & a
phosphonate (P=O) compound.
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I found this snippet on the Iraqi EMPTA VX process:
| Quote: | | O-ethyl methylphosphonothioic acid [EMPTA] on reaction with N,N-diisopropylethyl chloride in the presence of... |
The last part is likely a catalyst/acid acceptor. The net result is esterification of the EMPTA to form CV, the immediate precursor of VX that is
thermally isomerized to form VX.
To prepare EMPTA, TR (diester) is reacted with sulfur to form O,O-diethyl methylphosphonothioate. This is then half-hydrolyzed with NaOH to form the
half acid/half ester. The rest of the chemistry from there to VX is in the open literature (US3781387).[Edited on 27-6-2008 by Ritter]
[Edited on 28-6-2008 by Ritter]
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Sauron
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I will go retrieve the patent and post it here.
I think I see your point.
Saunders used dialkyl hydrogen phosphite to make the pentavalent dialkyl phosphonochloridate,
Hoechst made tervalent dialkoxychlorophosphine, and alkylated that via Grignard to TR. ((RO)2PMe)
OK, clear.
[Edited on 28-6-2008 by Sauron]
Attachment: US5128495.pdf (342kB)
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Sauron
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Here's a route to dichlor (DC, methyldichlorophosphine oxide) I'd forgotten:
(MeO)2P(=)-H -> (MeP(=O)(OH))2O
by heating to 300 C
Chlorination (classically by PCl5, other reagents are surely possible) gives MeP(=O)Cl2
Since DC can be thiated then dethiated to SW, this is potentially a route to both G and V agents.
See Saunders p.92-93.
Dimethyl hydrogen phosphite (for that is what it is) can also be exploited by conversion to the chloridate, then its sodium salt, reaction of the
sodium salt with MeCl to yield MeP(=O)(OMe)2 which can then be chlorinated, transesterified, etc. Classically, fluorinated directly to DF (MeP(=O)F2,
difluor) then partially esterified with the preferred alcohol (2-propyl, or pinacolyl, etc.)
These are most likely the 4-step and 5-step routes to GB mentioned briefly in Tucker's book.
[Edited on 28-6-2008 by Sauron]
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A preliminary mining of that manual for CWC inspectors, reveals complete structures or partial structures for:
VE
VG (Amiton)
VM
VS
VX
To which can be added VR "russian V-agent")
Structures for the above are in Wikipedia and are entirely consistent with information released in this manual.
and
V1
V2
V4
V5
Also PP-VX
These, AFAIK have not been described elsewhere. I cannot say whether the numbered V-agents precede VA or follow VZ. Insufficient information as yet.
V1 all we are told is that the ethanolamine is N,N-dimethyl. V2, N,N-diethyl. V4 and V5 have same ethanolamine as VX (N,N-di-isopropyl.)
PP-VX is a VX homolog where the alkyl group on P is n-propyl, all other elements of structure unchanged.
CWC defines V-agents in the schedule precisely.
R1 is alkyl in C-P bond where alkyl = methyl, ethyl, n-propyl or isopropyl
The two alkyl groups of the aminoethyl side chain are methyl, ethyl, n-propyl or isopropyl
The alkoxy group is up to C10. Cycloalkyls are included. No limitation on isomers is mentioned. This means that the number of alcohols possible is
quite large. But it is worth noting that in the case of VX the alcohol is ethanol. VX is allegedly yje most potent member of the series.
I would infer that there must exist a classified version of this manual, in which chemical weapons not declassified are described so that insectors
with appropriate clearance can be properly trained to look for indications of their development, manufacture, or stockpiling.
Most of those are not new revelations.
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| Quote: | Originally posted by Sauron
Here's a route to dichlor (DC, methyldichlorophosphine oxide) I'd forgotten:
(MeO)2P(=)-H -> (MeP(=O)(OH))2O
by heating to 300 C
Chlorination (classically by PCl5, other reagents are surely possible) gives MeP(=O)Cl2
Since DC can be thiated then dethiated to SW, this is potentially a route to both G and V agents.
See Saunders p.92-93.
Dimethyl hydrogen phosphite (for that is what it is) can also be exploited by conversion to the chloridate, then its sodium salt, reaction of the
sodium salt with MeCl to yield MeP(=O)(OMe)2 which can then be chlorinated, transesterified, etc. Classically, fluorinated directly to DF (MeP(=O)F2,
difluor) then partially esterified with the preferred alcohol (2-propyl, or pinacolyl, etc.)
These are most likely the 4-step and 5-step routes to GB mentioned briefly in Tucker's book.
[Edited on 28-6-2008 by Sauron] |
Now that we are exchanging graphic files, please send this type of contribution to me in that format.
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Sauron
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Here are the pages from Saunders on tabun and sarin. His graphical schemes are there. No need to redraw them.
There is a different path to the TR diester, not via SW, and one that is facile and employs no CWC scheduled reagents. I already sent you the details.
No PCl3, no Grignard. The plumbing may be exotic.
[Edited on 29-6-2008 by Sauron]
Attachment: Pages from phosphorus_fluorine_toxicity.pdf (152kB)
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| Quote: | Originally posted by Sauron
There is a different path to the TR diester, not via SW, and one that is facile and employs no CWC scheduled reagents. I already sent you the details.
No PCl3, no Grignard. The plumbing may be exotic.
[Edited on 29-6-2008 by Sauron] |
I have not received them. If you are referring to that U2U JACS ref, I'd appreciate receiving a pdf.
[Edited on 28-6-2008 by Ritter]
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Sauron
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I sent you complete citation of JACS article twice. by URL.
When I have the pdf I will post it here.
I posted pages from Saunders above.
So no need to draw graphical sceme again.
Methane and PF3 react (conditions not known yet) to form MePF2 and HF.
MePF2 reacts with ethanol (2 mols), product is TR diester.
This is right out of military manual.
See Brauer (forum library, Handbook of Preparative Inorg.Chem.) for prepn PF3; also different prep from JACS article I am waiting for.
Alkylation of PF3 higher or lower temp than PCl3? I don't know ywt. PF3 is as you would expect, a gas.
All information I have is from open sources. I am retired, and will not be filing any more patents. This is a chemistry forum. Anything we can discuss
between us we can post here. There's nothing confidential about any of this as far as I am concerned. Chemical journals, patent archives, books,
nothing secret or sinister. Unless libraries are sinister. Is knowledge sinister?
Sic gorgeamus a los subjectatus nunc.
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Ritter
Hazard to Others
Posts: 370
Registered: 20-6-2008
Location: Earth
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Mood: Curious
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| Quote: | Originally posted by Sauron
I sent you complete citation of JACS article twice. by URL. |
Not received here.
| Quote: |
When I have the pdf I will post it here.
I posted pages from Saunders above.
So no need to draw graphical sceme again.
Methane and PF3 react (conditions not known yet) to form MePF2 and HF.
MePF2 reacts with ethanol (2 mols), product is TR diester.
This is right out of military manual.
See Brauer (forum library, Handbook of Preparative Inorg.Chem.) for prepn PF3; also different prep from JACS article I am waiting for.
Alkylation of PF3 higher or lower temp than PCl3? I don't know ywt. PF3 is as you would expect, a gas.
All information I have is from open sources. I am retired, and will not be filing any more patents. This is a chemistry forum. Anything we can discuss
between us we can post here. There's nothing confidential about any of this as far as I am concerned. Chemical journals, patent archives, books,
nothing secret or sinister. Unless libraries are sinister. Is knowledge sinister? |
Sorry to bother you by sending you those graphic files. It won't happen again.
I worked the better part of my career in organofluorine chemistry & believe me, it is no improvement over the routes discussed earlier. HF &
fluoride ion are things to be avoided unless there is no other way to get there.
Ritter
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\"The production of too many useful things results in too many useless people.\"
Karl Marx
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Sauron
International Hazard
Posts: 5351
Registered: 22-12-2006
Location: Barad-Dur, Mordor
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Mood: metastable
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I can't understand why my PMs fail to reach you.
Phosphorus-Halogen Compounds from Phosphorus Pentoxide and Halides. Properties of Phosphorus Trifluoride and Phosphorus Oxyfluoride*
Grady Tarbutton, E. P. Egan, , Jr. S. G. Frary
J. Am. Chem. Soc.; 1941; 63(7); 1782-1789. DOI: 10.1021/ja01852a002
This paper teaches that PF3 and POF3 are produced in high yield by heating P2O5 and CaF2 (or other fluoride salts) as a solid mixture to 400-600 C.
The physical properties of these gases are described.
Analogously P2O5 and NaCl (yes table salt) produce POCl3 along with a small amount of PCL3 (10-25%) which appeared to be the result of reduction of
POCl3 by iron from the inner surface of the autoclave.
I agree with you about the "thrills" of working with HF neat. I did not say PF3 was an improvement as a starting material, only an alternative. As
this is a paper exercise such reagents are no barrier.
You should see the novichoks, really scary precursors there like carbonyl chloride fluoride oxime. Ugh.
I was not discomfitted about receiving your skc files. You asked me to regard them as confidential and NFP and so I shall. I simply asked why? As
nothing new seemed to be present.
Why don't you request the password for References from Polverone? It is a very useful resource. Also, write (PM) MadHatter and ask him to set up a
user account and pw for you for his ftp site. You will be surprised what a treasure trove is there.
This route to POCl3 and maybe PCl3 is one I have been sitting on for about a year. I have another back door method to POCl3 as well also from P2O5 but
the required reagent is costlier than NaCl.
[Edited on 29-6-2008 by Sauron]
Sic gorgeamus a los subjectatus nunc.
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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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| Quote: | Originally posted by Sauron
I was not discomfitted about receiving your skc files. You asked me to regard them as confidential and NFP and so I shall. I simply asked why? As
nothing new seemed to be present. |
Not to worry. I won't be sending you anything that I personally generate again. Personally-generated content is usually considered privileged if its
creator requests that status.
| Quote: | | Why don't you request the password for References from Polverone? It is a very useful resource. Also, write (PM) MadHatter and ask him to set up a
user account and pw for you for his ftp site. You will be surprised what a treasure trove is there. |
I may. This board is not very 'user friendly' in defining these options.
| Quote: | | This route to POCl3 and maybe PCl3 is one I have been sitting on for about a year. I have another back door method to POCl3 as well also from P2O5 but
the required reagent is costlier than NaCl. [Edited on 29-6-2008 by Sauron] |
I was hoping to collaborate with you on this topic since you & I seem to be the only ones here with the background & interests to contribute
anything of value. But as it seems that you are not really in a position to do so, no problem. Enjoy your retirement just as much as I am enjoying
mine.
[Edited on 28-6-2008 by Ritter]
[Edited on 28-6-2008 by Ritter]
Ritter
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\"The production of too many useful things results in too many useless people.\"
Karl Marx
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Sauron
International Hazard
Posts: 5351
Registered: 22-12-2006
Location: Barad-Dur, Mordor
Member Is Offline
Mood: metastable
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I spent 28 years as a very senior defense journalist - not because my background was journalism but because it was defense. You made no mention of
any proposed collaboration till now; in fact you said you were not writing a book on this. Oh, well, another chance at a Pulitzer down the crapper, I
suppose.
Here as promised is the JACS paper by Grady Tarbutton.
[Edited on 29-6-2008 by Sauron]
Attachment: tarbutton.pdf (807kB)
This file has been downloaded 512 times
Sic gorgeamus a los subjectatus nunc.
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