I�ve lurked as an unregistered user for awhile and hoping that I�m providing enough new information to make this post acceptable, even though it commits the double newbie faux pas of both asking a question and starting a new thread not in the watercooler.

I�ve searched the forum and found no reference to Hexanitroethane (HNE). It is reported to be a relatively stable solid with a fairly high melting point (~150C) as compared to Tetranitromethane�s (TeNM) 13.8C and a much lower vapor pressure. HNE has as much oxygen (O2) available for combustion as TeNM (~25 mole/liter when oxygen balanced to CO2 as compared to ~36 mole/liter for LOX).

I have found the following synthesis route to make it.

The Bromopicrin (tribromonitromethane) synthesis is from European Patent # WO2007023496, 03/01/2007, Oren, Golan, and Frim
The Dipotassium salt of Tetranitroethane (DKTeNEt) and the HNE syntheses are from the Encyclopedia of Explosives, 1974, Picatinny Arsenal and also referenced in Nitrocarbons, 1995, Nielsen. HNE data also from Physical and Chemical Properties of Hexanitroethane, AIAA Journal Feb. 1963, Nobel, et al.

Searches on SciFinder found no better synthesis routes.

My questions are:
a) does anyone have experience with any of these syntheses;
b) see any trouble spots
c) know of a better route

Thanks

Synthesis of Bromopicrin
Reactants: Nitromethane, Bromine, Sodium Hydroxide
Add 61g CH3NO2 (NM) to 100g water
Add 160g Br2 (~3:1 molar ratio with NM)
With continuous stirring, heat mixture to 35-40C
Slowly (~100g/hr) add 34% aqueous solution of NaOH until brown color disappears
Will take ~0.75g NaOH solution per gram of Br2
Important to keep stirring to not allow localized alkaline concentrations to build up causing side reactions
Continue stirring for 30 minutes and allow mixture to cool to room temperature
Allow organic and aqueous layers to separate. Organic layer will be almost pure Br3CNO2 with a yield >95%

CH3NO2 + Br2 to Br3CNO2

CAS# 464-10-8
MP: 10C
BP: 90C
SG: 2.79
Solubility: Water: 1.5g/l @20C



Synthesis of Dipotassium salt of 1,1,2,3-tetranitroethane (DKTeNEt)
Reactants: Bromopicrin, Potassium cyanide, potassium nitrite
50g Bromopicrin in 25ml MeOH
Add 25g finely powdered KNC
Add solution consisting of 12.5g KNO2 in 40ml water
Keep below 30C
Filter precipitate (DKTeNEt)
Dissolve crystals in slightly alkaline water and recrystallize
Dry at 80-90 Yield is ~35%
WARNING: dry material is an initiating explosive and extremely friction and impact sensitive.

2 Br3CNO2 + KCN to Br2(NO2)CC(NO2)Br2 + BrCN + KBr
Br2(NO2)CC(NO2)Br2 + 2 KNO2 to Br(NO2)2CC(NO2)2Br + 2 KBr

Yellow crystalline solid
MP: 293C (decomposes)
Impact Sensitivity H50: 8cm (2kg wt)


Synthesis of Hexanitroethane (HNE)
Reactants: DKTeNEt, Nitrating acid mixture
WARNING: impurities will cause material to explode on contact with concentrated sulfuric acid.
Dissolve 10g dry DKTeNEt in 50ml concentrated H2SO4 with constant stirring
Cool to 5C
Slowly add mixed concentrated H2SO4 and HNO3 (15ml each) with constant stirring and cooling
Slow raise temperature of mixture to 60-70.
Hold for 10 minutes
Cool in ice bath and drown in a large volume of ice water
Filter by suction and rinse with cold water
Dry with air
Dissolve in ether
Add CaCO2 and shake (neutralizes acid)
Filter and evaporate ether under vacuum

Br(NO2)2CC(NO2)2Br + 2 KCN to K(NO2)2CC(NO2)2K + 2 BrCN
K(NO2)2CC(NO2)2K to (NO2)2CHCH(NO2)2
(NO2)2CHCH(NO2)2 to (NO2)3CC(NO2)3

Colorless crystalline solid
MP: ~150C (decomposes)
Vapor Pressure: 0.5mm @ 25C
Density (compressed pellet): 1.88g/cm3 at 25C
Detonation Velocity: 4950m/s
Impact Sensitivity H50: 77cm (2kg wt)
Toxicity: High toxicity for repeated exposure to 3.0ppm

As mentioned in ''Die Chemie der Kapfstoffe'':
2 CBr3NO2 + 6KI + 2KNO2 --> C2K2(NO2)4 + 6KBr + 3 I2

so there is no need to use KCN or another CN(-) salt although its cheaper, easier to obtain and not kinda ''super poisonous'' ;)

PS: Synthesis of Dipotassium salt of 1,1,2,3-tetranitroethane (DKTeNEt)
there are no 3 carbons in ethane :p

CD-ROM-LAUFWERK: Sorry, 1,1,2,3 was a typographic mistake.

Hunter discusses using four different methods to obtain DKTeNEt. From Table II*, all methods started with 25g Bromompicrin:

KOH yielded 18g of crude product and 0.5g of pure salt
KI was 8.2g crude and 1.5g pure
KOet was 33g crude and 0.8g pure
KCN was 9.5g crude and 1.7g pure

(*Preparation and Reactions of Bromopicrin, Louis Hunter, Journal of the Chemical Society, Transactions, 1923, 543-549 � I can send a pdf copy to anyone who would like it)

I choose the KCN method as yielding maximum product, given the difficulty of the process. As it turns out, the KI method was easier

Further information:

The brompicrin synth was easy, followed exactly as outlined on the patent and yielded expected quantities.


The synthesis of DKTeNEt was much more problematic. The KCN addition created no issues, but the addition of the KNO2 aqueous solution generated significant quantities of heat. The only way to keep the temperature down (even in an ice-salt bath) was an addition rate of about 3 drops per minute. Temperature excursions favored side reactions and reduced the already minimal yield.

Eventually went to the KI method as it was less temperature sensitive.

Crude product from either route was messy and it was difficult to balance the quantity of water needed to dissolve the crude product and still crystallize out the pure salt. It took several attempts to get usable quantities of the pure salt. (These are photos of the crude).


Nitrating the DKTeNET with mixed acids was again straight forward.

The final Hexanitroethane was mixed in close-to stoiciometric ratios with nitromethane (8.8g HNE + 10.0g NM / OB~-1%) and ignited with a pyrotechnic initiator. The results were impressive.

The combustion chamber was machined from stainless steel with 10mm thick walls.



Needless to say, this is a sensitive mixture.

Work continues

When trying to view the attached files I get an error message reading "The image cannot be displayed, because it contains errors."

I got the same.

Plutobound, upload the pictures as a ZIP or RAR file to rapidshare and post the link here so we can see what you're talking about.

Sorry about that

http://rapidshare.com/files/29180182/Synth_photos.zip.html

Excuse me plutobound, "The Bromopicrin (tribromonitromethane) synthesis" ?

Bromopicrin seems a stuff something like an aromatic ester. BrC6H2(NO2)3.
I wan`t noting to say to this, every child what have somewhat knowledge in easy chemistry knows what give HBr and Benzene ? I think the result is Bromrobenzene, BrC6H5. Br2 and C6H6 should give Br3CH3 in a major concentration when it stirred on the boiling point of the benzene in an flask which is sealed easy with a glass wool stopper. I would mean you can make with a waste of bromine a slight access of C6Br6, C6HBr5 and CH26Br4 which you can separate by bp distillation when you have a pressure reflux quipment. The same things can you get when you handle the bromoethane with a waste of bromine. The major result should be 1,1,2,2-tetrabromoethane.

I have looked to found some boiling point of the bromo benzenes and ethanes to separate it by distillation.

bromrobenzene, boiling point around 156 degrees celsius
1,2 dibromobenzene, boiling point around 224 degrees celsius
1,3 dibromobenzene, boiling point around 188 - 219 degrees celsius
1,4 dibromobenzene, boiling point around 219 - 220 degrees celsius
1,2,4-tribromobenzne, boiling point - explosive or above 299 degrees celsius
1,3,5-tribromobenzne, boiling point around 271 degrees celsius

bromoethane, boiling point around 37 - 39 degrees celsius
1,2-dibromoethane, boiling point around 244 degrees celsius
1,1,2,2-tetrabromoethane, boiling point around 244 degrees celsius

The shitty databases gives nothing more to the boiling points of the in my opinion useful bromines.

A useful process is maybe when you 0,1 mol of bromoethane and 0,1 mol of the theoretical amount of HBr is refluxed above 244 degrees celsius some hours to 1,2-dibromoethane. The result is maked pure by disstillation and the distillate is than dropped in a chilled nitrating mixture of 0,8 mol triflouro actic acid anhydride and 0,4 mol of fresh distilled < 98 % HNO3 in a flask. Wehn you don`t hane TFAA, fresh concentrated H2SO4 and HNO3 should work too but the separation is more than crappy.
Next the flask is sealed with a glass wool stopper, the mix is stirred for one day at 39 to 40 degrees celsius and the remainders of TFAA and HNO3 are removed very careful by evaporation on a hotplate. The formed crystalls of 1,2-dibromo-1,1-2-2-tetranitroethane are careful collected and dissolved in 100 ml of fresh distilled EtOH and dryed ammonia is bubbled through the mix until the wight is increased the molar ratio to 1,2-diamino-1,1,2,2-tetranitroethane. It should work when you add more than 0,2 mol of 28 - 35 % ammonium hydroxide solution to the dissolved crystals and the solution is than stirred for four or five hours. The solution is than slowly concentrated on a stirrer by low heat to collect the crystals of 1,2-diamino-1,1-2-2-tetranitroethane.

I mean more than a probelm is the following fabrication of the hexanitroethane and not everybody have a lab equipment to prepare high nitrated stuff in a home lab.

Synthesis 1:
I think it`s esay to transfer the stuff into hexanitroethane when the collcted material is dissolved in a waste of concentrated HNO3 < 98%, collected crystals per 0,5 mol of acid and the mixture is stirred for 1 week or more at room temperature. The crystals of HNE are now collected when the remainders of the dilute HNO3 vaporaized very careful on a hotplate.
In my opinion a useful solvent to make the stuff pure is anhydrous EtOH. Maybe the crystals can be slowly dryed over anhydrous magnesium sulfate when somewhat wet.

Synthesis 2:
Dissolve the stuff of the collected crystals is a mixture of triflouro actic acid anhydride and HNO3 in a ratio 1:3:8 and stir the stuff for a week at room temperature rapidly. The crystals are colected by Synthesis 1. I mean a replacement to TFAA is TCAA - trichloro acetic acid anhydride when you have.

Synthesis 3:
The last way to make HNE is surely when the 1,2-dibromo-1,1-2-2-tetranitroethane is dissoveld in
concentrated H2SO4, < 98 % HNO3 is tropped in the mix, the mix is stirred for an hour and the material is then quickly extracted by several portion of methylene chloride.

I`ve thinking around by browsing the new papers of megas sites and every day i think, the ideas to get soemething are removing somewhat from me. Something is concocted in my simple mind !

My opinions are:
A simple stuff by preparing f.i. dnm or 1,1-dne --1 or 2 ne-(CH2)2 by
adding it to bleach:

results:
TNE(1,1,2,2) or TNP(1,1,3,3), results by (NO2)2=C-CH2 on waiting (1,1=C-C=3,3)TNEthen?

Why not HNE ? I`m to tired to think around with good stuff. :mad:

Always, the same pot- ? I mean 1,1,1-tne and tnm when traeted with bleach but gives hexanitroethane ! :eek:

Syth :??
Dissolve 1 g of 1,1,1-tne in 30 mL of MeOH (more than 5 mL of CH2CH2 ?)
By weight, add this to a warm solution of 2 g of tnm in 50 mL of MeOH and 1,5 g of NaOH.

Little precipitation of HNE should be filtered out by stirring it in on summer
day in an icy beaker of ice water..

How prepared 1,1,1-tne ? Questions like TNEtOH in megas pages, years ago to ?

It`s only a little upstairs to haven !

The main background of my oppinions are some stuff like this:
(CH3)NO2)C-C(NO2)(CH3) and so on !
Thinking like MeOH an PPTabs and more ?

What in gods name are you blathering about and does your doctor know you are off your meds? You are either using a bad machine machine translation, or you are retarded. Either way you are banned for being a danger to yourself and others.

Do not pay attention to this blather, the lack of coherent sentences makes it dangerous. Who knows what chemicals he is really talking about.

I am lord of the Syth?? :D