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Author: Subject: Halogenated Amines - the others
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[*] posted on 14-5-2008 at 00:41


Quote:
Originally posted by 12AX7
Wow, a synthesis using NI3.NH3, crazy!


I've found NI3.NH3 explodes readily like when being touched directly, bumped or scraped even under a lot of water. At some point, the weight of its own crystals should explode it in suspension. Iodine chloride would be the safer, albeit more toxic choice in a synthesis.
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[*] posted on 14-5-2008 at 04:57


I've seen reference to NI3.NH3 being used to convert acetylene to tetraiodoethylene as well.

This is regardig the chloramine analogue of PETN:

<b>Attempts toward the preparation of tetracyanomethane. Tetrakis(N, N-dichloroaminomethyl)methane, a very powerful explosive</b>. Gryszkiewicz-Trochimowski, Eustache; Gryszkiewicz-Trochimowski, Oleg; Levy, Robert S. Memorial des Poudres (1958), 40 109-12.
Abstract
C(CH2Br)4 was treated with p-MeC6H4SO2NH2, the resulting tetramide recrystd. with AcOH and hydrolyzed with H2SO4 to C(CH2NH2)4.4H2SO4 (I), m. 302-3. Treating I with a BaCl2 soln. and distg. the mixt. with solid KOH gave 54% C(CH2NH2)4.H2O (II), b15 147-9, m. 40-1. Heating slowly a mixt. of 6.2 g. II and 32 g. PhCHO (III) to 100 and keeping it at 100 1 hr. gave a yellow oil which solidified after H2O and excess III were removed in vacuo. Grinding with EtOH, drying, and washing several times with EtOH and petr. ether gave 16 g. C(CH2N:CHPh)4 (IV), m. 172-3 (1:1 tetrahydrofuran-Me2CO). NaOCl was prepd. by introducing the calcd. amt. of Cl into a cooled soln. of 18 g. NaOH in 85 cc. H2O. (Caution! Any free Cl must be removed by an air stream, otherwise spontaneous fires result on adding I.) To the cooled soln. was added 15 cc. glacial AcOH and then, with hand stirring, the total amt. of 4.5 g. I. The temp. was very slowly raised to 70-5 (it must not exceed 80). After several min., I dissolved and an oil formed. On rapid cooling in cold H2O, the oil solidified and the aq. layer was decanted. Washing with H2O, and drying first on paper then in a desiccator contg. H2SO4 gave 5.25 g. C(CH2NCl2)4 (V), m. 54-4.5 (Et2O-petr. ether). In storage, IV decompd. above -15 with evolution of Cl. It was believed that V exploded more vigorously on heating than Hg fulminate. Attempts to convert IV into C(CN)4 (VI) on heating to 300 in the presence of Pd gave only a small amt. of PhMe and an intractable residue. Attempts to convert V into VI by various dehydrochlorination procedures were fruitless. Thermal decompn. of V in (CH2Br)2 gave rise to the evolution of Cl instead of the expected HCl.
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Axt
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[*] posted on 10-7-2008 at 14:35


Quote:
Originally posted by Axt
Another OTC possiblility is the dichloramine of isopropylamine, which is available as "roundup" weed killer as the glyphosate salt. The chlorinated products of glyphosate (which is a secondary amine) should remain in solution.


The chlorination of monoisopropylamine glyphosate (roundup) failed. Roundup in 50% acetic acid was added to 12.5% NaOCl, a lot of gassing and foaming resulted with the distict smell of chloramine. No product separated, temperature wasnt monitored, but it only got slightly warm to the touch on addition. Isopropyldichloramine is known and its preparation is in JACS, 69 1539-40 (1947):

"i-Propyldichloramine was prepared by a modification of the above procedures. To an ice-cooled concentrated aqueous solution of 95 g. (I mole) of i-propylamine hydrochloride (prepared in situ) was added slowly 2.25 moles of aqueous sodium hypochlorite (prepared by adding chlorine to cold 15% aqueous sodium hydroxide, 1.6 moles hypochlorous acid per liter). Simultaneously with this addition over two to three hours was added 6 N hydrochloric acid at such a rate that the acidity was maintained between pH 5.6 and 6.6. Bromcresol green and chlorphenol red papers can be used as criteria if the solution is allowed to creep into the paper so as to give an indicator zone ahead of the bleached zone. After two hours' subsequent stirring in the cold, the heavy oil was separated, washed once with 30 cc. cold water, twice with 50-cc. portions of 5% sodium thiosulfate, once with cold water, twice with cold 50% sulfuric acid and finally twice with cold water. The crude yield (97 g., 76% of theoretical) contained 94% of the theoretical electropositive chlorine content. Distillation at 41-43' (15 mm.) resulted in 70% recovery of yellow oil (d20/4 1.165; n23D 1.4572) which contained 99.8% of the calculated electropositive chlorine content."

Depending on how readily glyphosate is chlorinated it might just be a case of it using up all the NaOCl. http://cat.inist.fr/?aModele=afficheN&cpsidt=18092577
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[*] posted on 10-7-2008 at 14:56


The tetrabrominated derivative of ethylenediamine was prepared. Its mentioned in the JCS article I attached into this thread, by adding ethylenediamine to hypobromous acid. I formed this in situ by adding NaBr to NaOCl.

12g acetic acid was added to 2g ethylenediamine in 12ml water. This was then slowly poured into a cooled solution of 28g sodium bromide in 140ml 12.5% sodium hypochlorite. An orange precipitate formed immediately on addition that was filtered. Dissolving the precipitate in DCM in which it is very soluble and evaporating gave brilliant orange crystals having the melting point reported in the literature (62°C).

It ignited with a fssht with a fair quantity of smoke. Heating on a spoon it first melted the puffed off. It explodes readily when struck with a hammer on steel. I wasnt prepared to heat more then a pinch at a time since the JCS article mentions a "very violent detonation" on heating, they dont mention the conditions but thats likely under confinement.

[Edited on 11-7-2008 by Axt]

tetrabromoethylenediamine-precip.jpg - 30kB
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[*] posted on 10-7-2008 at 22:54


Concerning the literature descriptions, many times small details are left out, this is the thing I hate most about it. Nice crystals.
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[*] posted on 11-9-2008 at 00:50


Taking it to another level of power and instability are N-perchlorylamines. There are not many are well known, besides N-perchlorylpiperidine, C5H10NClO3, which US 3332955 describes as a dangerously sensitive oil and perchlorylamide salts.

Reactions of Dichlorine Heptoxide with Amines:
http://pubs.acs.org/cgi-bin/abstract.cgi/jacsat/1974/96/i10/...
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[*] posted on 19-10-2008 at 09:55


Does N-tetrabromoethylenediamine work as a complexing agent? I figure each of the 4 N atoms has a lone electron pair.
[(Br2N-CH2-CH2-NBr2)2Cu](ClO4)2 looks interesting...
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[*] posted on 29-10-2008 at 03:44


I had tried to complex the tetrachloro compound, but to no avail. I mentioned the attempt on first page of this thread by mixing a DCM solution of TCED with a water solution of copper sulphate, there was no noticable change in the two layers.
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[*] posted on 24-12-2008 at 01:23


Here's another one. It is the most basic organic chloramine from what I can tell and quite unstable. Methylenechloroamine CH2=NCl made from action of formaldehyde onto chloramine in water solution which results from NH4Cl and NaClO (Cross, Bevan, Bacon, Journal of the Chemical Soc. of London. 97, 2406). Needles (from CHCl3). It is very unstable in air. Decomposes at 50-60°C explosively under formation of NH4Cl. Soluble in 20-30 parts ether at room temperature. In benzene it appears to polymerize.
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[*] posted on 25-12-2008 at 16:34


More references on the above here and here (pg. 12).
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[*] posted on 25-12-2008 at 19:57


I have the original french article for what that is the abstract of. I have tried to form the RDX analogue once, though failed. I no longer know the exact process I tried.

I OCR'ed and added the machine translation to the end.

Attachment: Cyclotrimethylenetrichloramine - Bull. Soc. Chim. Fr., 9, 1025 (1911) w translation.pdf (280kB)
This file has been downloaded 876 times

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[*] posted on 26-12-2008 at 00:52


Thank you for that paper. I forgot to add that Cross also patented a method for the preparation of the monomer compound in English pat. 15303 (1909). No idea where to get this though.
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[*] posted on 22-1-2009 at 13:01


From the citation above by Formatik
http://www.rsc.org/delivery/_ArticleLinking/DisplayArticleFo...
on pg 12

Action of Sodium Hypochlorite on Hexamethylenetetramine.

MARCEL DELEPINE ( Bull. Soc. chim., 1911, [IV], 9, 1025--1029 ).
Sodium hypochlorite reacts with aqueous solutions of
hexamethylenetetramine to form N-Dichloropentamethylenetetramine,
but in presence of acetic acid gives N-trichlorotrimethylenetriamine
( 1,3,5-trichlorohexahydrotriazine ), which is isomeric with Cross,
Bevan, and Bacon's methylenechloroamine ( Trans,, 1910, 97, 2404).
N-Dichloropentamethyenetetramine, C5H10N4CI2, crystallises in brilliant
lamellae: from water, or in octahedra from ether, possesses the odour
peculiar to compounds containing chlorine and nitrogen, is sparingly
soluble in water, and moderately so in ether or benzene, and deflagrates
at 78-82', giving an odour of carbylamines. It can be kept for long
periods in sealed tubes, but decomposes in the course of a, few days on
exposure to air, forming ammonium chloride and hexnmethylenetetramine
hydrochloride. With sodium hydroxide in alcohol, ammonia is produced,
and the chlorine is removed as alkali chloride.
1,3,5-Trichlorohexahydrotriazine ( Abstr., 1899, i, 326 ),
. .NCl --- CH2
. . / . . . . . . . \
CH2 . . . . . NCl
. . \ . . . . . . . /
. .NCl --- CH2
crystallises in brilliant needles, has a slight odour of chlorine, is nearly
insoluble in water, but soluble in alcohol or chloroform, and deflagrates at
78 º, evolving fumes having the odour of hydrogen cyanide and carbylamines,
and leaving a residue of ammonium chloride. It decomposes in air, or when
kept in solution in organic solvents. With sodium hydroxide in alcohol,
it yelds ammonia and sodium chloride, and the residue on distillation
with a dilute acid gives formic acid : this decomposition
appears to take place in accordance with the equations :
(1) (CH,:NCl), + 3NaOEt = 3NaC1+ 3CH(NH)*OEt ;
(2) CH(NH)*OEt + 2H20 = H*CO2H + EtOH + NH2.
T. A. H.

_________________________________________


The above cited paper on Methylenechloramine was obtained for me by solo some time ago,
Chloroamine Reactions :Methylene chloroamine
http://www.sciencemadness.org/talk/viewthread.php?tid=9319&a...
it is also available here. http://ifile.it/yjwc4in

My research on chloramine production
http://www.sciencemadness.org/talk/viewthread.php?tid=6042&a...
Ironically I just found this thread relating experiences with a likely method
for production of choramine (NH4)2SO4 + Ca(ClO)2 -> CaSO4•2H2O + 2 H2NCl
http://www.sciencemadness.org/talk/viewthread.php?tid=2567
I had independently thought of using the measured amount of this in a chlorinated
organic solvent for anhydrous production of chloramine, to then react with formaldehyde
to form Methylenechloramine as described in the paper above. A small beaker of the
wetted mixture would be placed inside a larger canister with a airtight lid
( something like tupperware ) containing about two centimeters deep of formaldehyde.

I thought that the method described in this paper here for C - nitration could
perhaps be also applied to N - nitration
A New Method for the Synthesis of Aliphatic Nitro Compounds1, 2.
http://sciencemadness.org/talk/viewthread.php?action=attachm...
Another german paper on just this idea posted by Axt in his Azidamine thread
Nukleophile Substitutionen an N-Chlor-aminen
http://www.sciencemadness.org/talk/viewthread.php?action=att...

Additionally here is a theoretical study on Methylene Nitroamine
the supposed monomer of the familiar RDX trimer. It has not been isolated
and is supposed a decomposition intermediate of RDX.
Analytical Potential Energy Surface for Methylene Nitramine (CH2NNO2)
Re-direct > http://handle.dtic.mil/100.2/ADA291247
to this download link _
http://www.dtic.mil/cgi-bin/GetTRDoc?AD=ADA291247&Locati...

Also contained in the zip file below with three other patents is this one , Perchloramide NClO3 US pat3295933
The literature on this substance is scant, but the described double salt NH4.HNClO3•NH4F
should react with formaldehyde in the expected manner forming an organic compound.

Nicodem provided this abstract for chlorinating Melamine in my Amine Methathesis thread
http://www.sciencemadness.org/talk/viewthread.php?tid=6717&a...
This zip file contains the above cited patent and these following patents relating to Hexachloromelamine.
Hexachloramine prep GB815682 , Hexachloromelamine US2472361 , Hexachloromelamine US3364214
http://ifile.it/tbvopum

len1 details proceedures for chlorine production
http://www.sciencemadness.org/talk/viewthread.php?tid=9713
The applicable chlorine threads
http://www.sciencemadness.org/talk/viewthread.php?tid=1305
http://www.sciencemadness.org/talk/viewthread.php?tid=730

.
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[*] posted on 7-6-2011 at 19:06


Would reacting difluoramine, HNF2, with methyl perchlorate, CH3OClO3, dissolved in a solvent to prevent it from exploding, produce (CH3)2NF2[+] [-]ClO4 ?
Might be an interesting energetic compound, decent oxygen balance.

Dimethyl sulfate is known to be a potent alkylating agent, easily methylating amines to quaternary amines, so one would think methyl perchlorate, despite being extremely sensitive, would also work.

Some more information about HNF2,
http://pubs.acs.org/doi/abs/10.1021/ja01505a009

http://docs.google.com/viewer?a=v&q=cache:UuOX44kUhKgJ:w...

Also some articles about alkylating fluoramine and difluroamine:
http://www.springerlink.com/content/x032141571015122/

http://pubs.acs.org/doi/abs/10.1021/ja01003a021

http://pubs.acs.org/doi/abs/10.1021/jo01259a004

this is not really a direct alkylation, but also perhaps interesting:
http://docs.google.com/viewer?a=v&q=cache:RvwI9l1J6sEJ:w...

[Edited on 8-6-2011 by AndersHoveland]




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[*] posted on 8-6-2011 at 03:03


I wonder what is the result of the action of a base on such chloramines...
Does someone have infos on that?

R-NCl2 + 2 NaOH --> R-N(OH)2 + 2 NaCl
R-N(OH)2 --> R-N=O + H2O

Might be very valuable if it works... :cool:
H2N-CH2-CH2-NH2 -Cl2-> Cl2N-CH2-CH2-NCl2
Cl2N-CH2-CH2-NCl2 -NaOH-> O=N-CH2-CH2-N=O
O=N-CH2-CH2-N=O <==> HO-N=CH-CH=N-OH




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[*] posted on 9-6-2011 at 13:46


The reaction between a base and chloramines is likely very slow without heating. Hypochlorite is produced, which would likely oxidize any intermediate nitroso groups to nitro.
For example, I think the reaction between nitrogen trichloride and aqueous base is:
(4)NCl3 + (18)OH[-] --> (3)Cl[-] + (9)OCl[-] + (9)H2O + (2)N2

Nitrogen trichloride is hydrolyzed by hot water.
Nitrogen trifluoride is inert to pure water at 133° C but reacts slowly with aqueous base at 100° C to give nitrite and fluoride. NF3 is also hydrolyzed by hot salt water, or hot hydrochloric acid, but not by dilute sulfuric acid.
http://docs.google.com/viewer?a=v&q=cache:vkG5Vh7ZuWEJ:w...

Information about the preparation of compounds containing the tris(difluoramino)methyl group:
http://www.freepatentsonline.com/3758555.html

Although --NF2 groups make energetic compounds more sensitive, geminal --NF2 groups (two difluoramino groups on the same carbon atom) are much more thermally stable than geminal nitro groups.

Preparation of Difluoramine HNF2
The aqueous fluorination of urea to N,N-difluorourea (H2NCONF2) gives highest yields at a pH range between 4 to 8. Using highly concentrated alkaline solutions instead gave tetrafluorohydrazine (N2F4), wheras only moderately basic solutions did not favor formation of any products that contained N-F bonds.
Difluorourea was isolated from the reaction mixture by five successive extractions of the cold, aqueous solution of fluorinated guanidinium hydrofluoride with ethyl acetate. After the first extraction, only one fourth of the volume of initial solvent is used. The combined portions of extraction solvent were dried with anhydrous sodium sulfate and the solvent evaporated at room temperature. The residue remaining after evaporation of the solvent was subjected to reduced pressures of less than 1 mm Hg, the difluorourea evaporated from the residue and was condensed at (minus) -15 degC. Through repetition of the sublimation process and using fractional condensation of the evaporating material to effect separation from water and acetic acid, difluorourea was isolated as a white, crystalline solid, with a melting point of 42 - 44 degC.

The difluorourea is not isolated, but is converted to difluoramine by direct addition of mineral acid to the aqueous solution of fluorinated guanidine hydrofluoride (or of fluorinated urea) followed by heating the solution to drive off the difluoramine, which is then collected by cold condensation. The yields of pure difluoramine from this procedure are 10 - 15% of the theoretical amount. Traces of perfluoroguanidine gas, which could later be condensed at around -195 degC, are also given off by the reaction. V. Grakauskas, K. Baum. Journal American Chem. society. volume 92, p2096. (1970)

[Edited on 9-6-2011 by AndersHoveland]




I'm not saying let's go kill all the stupid people...I'm just saying lets remove all the warning labels and let the problem sort itself out.
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