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Author: Subject: C.T.M.T.N.A (R-salt)
Boffis
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[*] posted on 7-2-2013 at 06:27


Has anybody ever tried oxidizing nitroso R salt with oxone with or without the presence of acetone? This seems to be the miracle oxidant for most things.
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Rosco Bodine
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[*] posted on 26-4-2013 at 10:47
R-salt as reagent for nitrosation of hydrazine?


Today I have been wondering what may be the result of reacting R-salt with hydrazine. Nitrosamines can react with hydrazine to form the azide group or free hydrazoic acid.
For example diphenylnitrosamine reacts with hydrazine in the presnce of sodium hydroxide to form sodium azide while the reacting nitrosamine precursor is reduced to the amine. The scenario is one where the nitrosamine acts as a reagent for nitrosation or diazotization. I have speculated before that R-salt may have usefulness as a reagent for nitrosation and it could possibly work for such purpose. See attached patent DE273667 for reference for the diphenylnitrosamine reaction with hydrazine.

Attachment: DE273667 Staudinger Azide from nitrosamine and hydrazine patent.pdf (104kB)
This file has been downloaded 544 times

[Edited on 27-4-2013 by Rosco Bodine]
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Boffis
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[*] posted on 26-4-2013 at 14:23


@ Rosco

What an interesting idea, I have a try at this one when I get home. The result I guess would be 1 mole of triazine and 3 of sodium azide per mole of CTMTNA. I'll translate the patent tonight if I get time it's only 2 pages, I'm working on the Curtis paper from the azide thread at present but 25pages is heavy going. The advantage of diphenylamine appears to be it ease of recycling, I'm not sure that this nitroso compound will be recyclable though its easy enough to prepare from hexamine.
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Rosco Bodine
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[*] posted on 26-4-2013 at 16:49


Yeah that is how I see it, one mole of R-salt should do the same nitrosation as would require 3 moles of diphenylnitrosamine, for having 3 nitrosamine groups on the R-salt compared to the 1 of diphenylnitrosamine.

It is intriguing what may result and I can find nothing instructional in the literature. It would seem on first glance that the R-salt would simply be reduced to hexamine from which it came, and that would be the byproduct of using R-salt as a nitrosating agent for the hydrazine. I would amend that first impression after reviewing the structure, and seeing that it will not occur that hexamine will be the byproduct because the original hexamine structure was lost in the synthesis of the trimethylene structure of R-salt. The likely byproduct of nitrosation would seem to be probable trimethylenetriamine. Not being sure what would be the hydrolytic stability of the R-salt, nor knowing what the kinetics would be, it could be a "dump in a lump" scenario for the addition of the R-salt, or incremental addition where one would work better or equally well being an unknown.

Also there is the matter of the R-salt decomposition trimethylenetriamine byproduct being separated or decomposed or perhaps just left in solution, it would depend upon what is intended later for isolation of the ultimate intended product. It just seemed like a possible good candidate for an aqueous reaction system which could produce a decent yield of azide.

I have attached a fair amount of documents into the azide thread recently, and I am still reading and requesting yet other references and abstracts. Thanks for any help with insight from the translations of especailly interesting parts. Azides are a bit of very interesting chemistry which overlaps the inorganic and organic realm.

Analogously the R-salt may also serve to nitrosate hydrazodicarbonamide (biurea) which should have some solubility in alkaline solution.

Similarly R-salt may nitrosate acetone azine or methyl ethyl ketazine in aqueous alkaline solution.

Possible experiments here :D I think 'em up don't I ? :D

[Edited on 27-4-2013 by Rosco Bodine]
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Boffis
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[*] posted on 26-4-2013 at 19:03


Yep, Iève been thinking about this too and I think you are right about the hydrolytic stability of the byproduct cyclo-trimethylenetriamine. It is likely to break down into formaldehyde and ammonia both of which are volatile and would be removed with the alcohol (and then recombine to form hexamine and excess ammonia) leaving behind relatively pure sodium azide. Mmmmmm sound too good to be true(!) but certainly worth trying. I wonder if dimethylnitrosamine would work? then the freed amine would certainly be volatile with the alcohol.

Here's the translation of Staudinger's patent (btw where did the number DExxx come from? The pat number in the document is different.





[Edited on 27-4-2013 by Boffis]

Attachment: Hydrazoic acid & azide salts from hydrazine & nitrosamines H Staudinger 1913 Patent DE273667 English.docx (15kB)
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Rosco Bodine
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[*] posted on 26-4-2013 at 19:39


DE205683 is the Stolle azide patent that DerAlte and I have already translated, so you got your wires crossed there. The Staudinger patent above is the nitrosamine plus hydrazine related patent DE273667 also same on the patent.
Staudinger is simply referencing the earlier Stolle patent as prior art. So there's your confusion. Just edit the main number to DE273667.

Thanks Boffis for translation of the patent. I changed the formatting slightly to fit it on a single page and made a pdf for it too. (attached)

Urbanski 3 has a writeup on R-salt that provides useful information about the hydrolytic properties (attached)

The Bachmann and Deno JACS article also mentioned earlier in the thread is attached

Here also is an R-salt synthesis which I am not certain but I don't recall being posted before. From Journal of the Chemical Society 1889



Attachment: German Patent 273667 A method for producing hydrazoic acid or azide salts.pdf (45kB)
This file has been downloaded 618 times

Attachment: R-salt preparation JCS.pdf (164kB)
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Attachment: Nitrosamine pages from Urbanski 3.pdf (273kB)
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Attachment: Bachmann and Deno JACS nitrosation of hexamine.pdf (395kB)
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[Edited on 27-4-2013 by Rosco Bodine]
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[*] posted on 6-4-2014 at 12:16


Does anyone happen to know the approximate "self-life" of stabilized R-salt? If not can anyone lead me in the right direction to calculating it?
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Rosco Bodine
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[*] posted on 6-4-2014 at 12:36


What exactly is "stabilized" R-salt ? Please be more specific.
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[*] posted on 6-4-2014 at 14:28


IIRC, R-Salt can have a stabilizing effect on nitric esters (nitrated polyols).

Would like to confirm that, will come back with sources once I find them, if no one beats me to the punch.

EDIT: Relavent quote found, as suspected, Rosco himself!

Quote: Originally posted by Rosco Bodine  
From the information in the Bachmann & Deno article it appears that use of acetic acid takes the pH too far in the wrong direction for R-salt and leads instead to the DPT material which is primarily useful as a precursor for HMX . The DPT is obtained in better yield more cheaply by simply using less HCl to raise the pH of the
reaction mixture , so acetic acid offers no advantage .

PATR states that a mixture of R-salt and NG kept at 90C for 5 days showed no apparent decomposition ? Possibly a misprint , because that would seem to indicate stabilizing properties for R-salt towards nitroesters which if true is very interesting . If this is general , R-salt could possibly have value as an energetic stabilizer as well as filler for ETN melt and other low melting compositions , and possible usefulness in many other nitroester containing compositions .


[Edited on 6-4-2014 by packetforger]
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Rosco Bodine
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[*] posted on 6-4-2014 at 15:03


That information was from PATR and identified as a possible error / misprint. I never tested the reported R-salt use as a stabilizer or looked into further. That reference was something that was referencing a possible anomaly where the R-salt would be acting as the stabilizer, or there could be a reciprocal stabilizing effect, but I never found anything further about that or determined by any experiments if it is even true or is a misprint. I remain skeptical and would guess it is probably a misprint.

[Edited on 6-4-2014 by Rosco Bodine]

Attachment: R-salt pages from PATR Vol. 3 C (cont.)-D.pdf (389kB)
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[*] posted on 19-4-2014 at 09:55


Sorry about that. I'm curious on what the general "Shelf-life" of r-salt is.
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Rosco Bodine
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[*] posted on 19-4-2014 at 10:35


3-5 years under mild storage conditions
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[*] posted on 21-4-2014 at 00:50


Washed only material turned to something like hexamine after 1 year of room temperature storage and some time at elevated temperatures. Also, I've heard it's difficult to set off generally, so it's not a good cap basecharge option.
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[*] posted on 27-8-2015 at 06:08
1,3,5-Trinitroso-1,3,5-triazinane (R-Salt)


1,3,5-Trinitroso-1,3,5-triazinane

Molecular Formula C3H6N6O3
Average mass 174.118 Da
Monoisotopic mass 174.050140 Da
ChemSpider ID 24566
Log Octanol-Water Partition Coef (SRC):
Log Kow (KOWWIN v1.67 estimate) = -1.78

Boiling Pt, Melting Pt, Vapor Pressure Estimations (MPBPWIN v1.42):
Boiling Pt (deg C): 407.93 (Adapted Stein & Brown method)
Melting Pt (deg C): 145.55 (Mean or Weighted MP)
VP(mm Hg,25 deg C): 7.75E-007 (Modified Grain method)
Subcooled liquid VP: 1.29E-005 mm Hg (25 deg C, Mod-Grain method)

Water Solubility Estimate from Log Kow (WSKOW v1.41):
Water Solubility at 25 deg C (mg/L): 1e+006
log Kow used: -1.78 (estimated)
no-melting pt equation used

Water Sol Estimate from Fragments:
Wat Sol (v1.01 est) = 1e+006 mg/L

ECOSAR Class Program (ECOSAR v0.99h):
Class(es) found:
Aliphatic Amines

Henrys Law Constant (25 deg C) [HENRYWIN v3.10]:
Bond Method : 1.69E-008 atm-m3/mole
Group Method: Incomplete
Henrys LC [VP/WSol estimate using EPI values]: 1.776E-013 atm-m3/mole

Log Octanol-Air Partition Coefficient (25 deg C) [KOAWIN v1.10]:
Log Kow used: -1.78 (KowWin est)
Log Kaw used: -6.161 (HenryWin est)
Log Koa (KOAWIN v1.10 estimate): 4.381
Log Koa (experimental database): None

Probability of Rapid Biodegradation (BIOWIN v4.10):
Biowin1 (Linear Model) : -0.9088
Biowin2 (Non-Linear Model) : 0.0001
Expert Survey Biodegradation Results:
Biowin3 (Ultimate Survey Model): 1.6590 (recalcitrant)
Biowin4 (Primary Survey Model) : 3.6520 (days-weeks )
MITI Biodegradation Probability:
Biowin5 (MITI Linear Model) : -0.3603
Biowin6 (MITI Non-Linear Model): 0.0000
Anaerobic Biodegradation Probability:
Biowin7 (Anaerobic Linear Model): 0.4760
Ready Biodegradability Prediction: NO

Hydrocarbon Biodegradation (BioHCwin v1.01):
Structure incompatible with current estimation method!

Sorption to aerosols (25 Dec C)[AEROWIN v1.00]:
Vapor pressure (liquid/subcooled): 0.00172 Pa (1.29E-005 mm Hg)
Log Koa (Koawin est ): 4.381
Kp (particle/gas partition coef. (m3/ug)):
Mackay model : 0.00174
Octanol/air (Koa) model: 5.9E-009
Fraction sorbed to airborne particulates (phi):
Junge-Pankow model : 0.0593
Mackay model : 0.122
Octanol/air (Koa) model: 4.72E-007

Atmospheric Oxidation (25 deg C) [AopWin v1.92]:
Hydroxyl Radicals Reaction:
OVERALL OH Rate Constant = 242.3450 E-12 cm3/molecule-sec
Half-Life = 0.044 Days (12-hr day; 1.5E6 OH/cm3)
Half-Life = 0.530 Hrs
Ozone Reaction:
No Ozone Reaction Estimation
Fraction sorbed to airborne particulates (phi): 0.0909 (Junge,Mackay)
Note: the sorbed fraction may be resistant to atmospheric oxidation

Soil Adsorption Coefficient (PCKOCWIN v1.66):
Koc : 911.8
Log Koc: 2.960

Aqueous Base/Acid-Catalyzed Hydrolysis (25 deg C) [HYDROWIN v1.67]:
Rate constants can NOT be estimated for this structure!

Bioaccumulation Estimates from Log Kow (BCFWIN v2.17):
Log BCF from regression-based method = 0.500 (BCF = 3.162)
log Kow used: -1.78 (estimated)

Volatilization from Water:
Henry LC: 1.69E-008 atm-m3/mole (estimated by Bond SAR Method)
Half-Life from Model River: 4.572E+004 hours (1905 days)
Half-Life from Model Lake : 4.988E+005 hours (2.078E+004 days)

Removal In Wastewater Treatment:
Total removal: 1.85 percent
Total biodegradation: 0.09 percent
Total sludge adsorption: 1.75 percent
Total to Air: 0.00 percent
(using 10000 hr Bio P,A,S)

Level III Fugacity Model:
Mass Amount Half-Life Emissions
(percent) (hr) (kg/hr)
Air 0.044 1.06 1000
Water 58.9 4.32e+003 1000
Soil 41 8.64e+003 1000
Sediment 0.116 3.89e+004 0
Persistence Time: 992 hr


CTMTNA.png - 14kB




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Boffis
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[*] posted on 16-1-2021 at 04:14


Regarding the stability of this compound, I have just come across the jar of recrystallised material figured in my post above and the beautiful yellow crystals are in apparently perfect condition with no signs of degradation. So it would appear that properly purified and stored in a cool dry place in a tightly closed jar it is certainly stable for at least 8 years.
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