Sciencemadness Discussion Board - peroxide_nitramine?

peroxide_nitramine?

KABOOOM - 24-9-2002 at 18:43

These are just my thoughts

1. make a solution of a nitrate salt(better NaNO3) in 98% H2SO4
2. add urea to the previous solution to get dinitrourea, pour in another backer with crashed ice inside

3. make a solution of formalin & H2O2 and chill it in ice bath

4. mix the two solutions to get (something like

tetramethylene diperoxide dinitramine!

O O
// //
2H2SO4 + 2NaNO3 + HN--N--C => 2NaHSO4 + 2H2O + O2N--N--C dinitrourea
/ \ / \
H N--H H N--NO2
\ \
H H

O
//
O2N--N--C + H2O => CO2 + 2 O2N-NH2 nitramide
/ \
H N--NO2
\
H

O O - O
// / \
2 H-C + H2O2 => H2C CH2 formaldehyde peroxide
\ \ /
H OH HO

O - O H2C-OO-CH2
/ \ / \
2 O2N-NH2 + 2 H2C CH2 => O2N-N N-NO2 T.M.D.D.N.A
\ / \ /
OH HO H2C-OO-CH2

the structure shows the properties of the explosive!

Note: use much more than 4mol H2SO4 per 1mol urea (thats because of the H2O produced)

I was thinking about organic peroxides containing nitro ,nitrate or
nitramine group, when I found such a compound probably could exist (I'm not still sure)
I will try it as soon as I get H2SO4 :cool:

sssh..

KABOOOM - 24-9-2002 at 18:48

I can't edit
if you want two see the formula go to My briefcase

Ramiel - 25-9-2002 at 05:08

link doesn't work for me.

ps. more than one space gets deleted. hahahahhahaha. I bet you spent so looong on that eh?

Rhadon - 25-9-2002 at 08:12

You cannot publish direct links to files in your briefcase anymore since they are time limited now.

KABOOOM - 26-9-2002 at 19:12

madscientist - 26-9-2002 at 20:09

You might want to consider using one of these free web hosting services:

www.netfirms.com

free.prohosting.com

sitebuster - 11-10-2002 at 01:55

Is it possible,
to use the follow to make a peroxide ?

epoxycyclododecane
C2H22O

KABOOOM(pyrojustforfun) - 12-10-2002 at 18:32

I am the same person made the topic but I had to make another account
and sorry for the delay
my pc motherboard was damaged
it seems angelfire has changed the pic or something like that,(meant the img src address was right) you probably could see the correct pic by a right click on the pic => properties => copy the address => paste on your browser's address bar => Enter !
if it didn't work too use your mind! imagine a hmtd molecule that one of the -CH2-OO-CH2- chains
is replaced with two -N-NO2
the process is like the reaction between formaldehyde peroxide & NH3 or urea that yields into HMTD & TMDD
HMTD: 3 HO-CH2-O-O-CH2-OH + 2NH3 => N(-CH2-O-O-CH2-)3N + 6 H2O
TMDD: 4 HO-CH2-O-O-CH2-OH + O=C(-NH2)2 => O=C(-N(-CH2-O-O-CH2-)2N-)2C=O
TeMDDNA: 2 HO-CH2-O-O-CH2-OH +2 H2N-NO2 => 2ON-N(-CH2-O-O-CH2-)2N-NO2

TeMDDNA.gif - 21kB

vulture - 13-10-2002 at 02:24

IIRC, formaldehyd peroxide (like all aldehyde peroxides) is too unstable to exist. Try a workaround from Hexamethylenetetramine or formaldehyde + NH_3>

Free Picture Hosting Services

Psycho - 13-10-2002 at 12:51

Many of the major websites that have free hosting services do not allow you have direct links to your pictures. Such websites include Angelfire, Geocities, etc.

Psycho - 13-10-2002 at 13:01

Use the < pre > < /pre > tags when drawing structual formulas, such as the ones you were drawing in this post.

I hope this works, it should since HTML is On.

Before

H H
\ /
O

After



 H    H

  \  /

   O

KABOOOM(pyrojustforfun) - 13-10-2002 at 17:32

edit: the tmdd formula was wrong, it's like this: O=C(-NH-CH2-O-O-CH2-NH-)2C=O
I also didn't write the H2O by Product(which is not important!)

PHILOU Zrealone - 5-3-2003 at 02:51

HEMEX group (High Energetic Material EXplosive) was studying DNU and they attempted the reaction with CH2=O... you get instantaneous polymerisation and precipitation of ureaformol polymer...the polymer didn't seem to have any inflamability or explosive properties!

Urea complexate H2O2 to make NH2-CO-NH2.H2O2!
CH2=O doesn't survive long H2O2 in strong acidic media!
NH2-NO2 self oxydate fast into N2O and H2O!
NH2-NO2 + CH2=O --> HMX and RDX but in acidic media you get decompositions!

Thus the reaction between RDX or HMX in the neutral and H2O2 might give your molecule!

Do you have properties datas or infos on
TMDD?
The molecule you draw:
O=C(N(-CH2-O-O-CH2-)2N)2C=O
Is Octa Methylene Tetraperoxyde Diurea (OMTD)!

KABOOOM(pyrojustforfun) - 13-3-2003 at 19:33

what if one could isolate dimethylol peroxide(other names are di(hydroxymethyl)peroxide or DHMP) or methylol hydroperoxide (hydroxymethyl hydroperoxide or HMHP or MHP)
<a href="http://ies.jrc.cec.eu.int/Units/cc/events/torino2001/torinocd/Documents/Anthropogenic/AP39.htm">Tropospheric Reactivity of Organic Hydroperoxides</a>
HCHO + H2O    qe   H2C(OH)2
Formaldehyde peroxidation
H2O2 + H2C(OH)2   qe   HOCH2OOH + H2O
HOCH2OOH + H2C(OH)2   qe   HOCH2OOCH&l t;SUB>2OH + H2O
from <a href="http://www1.xlibris.com/bookstore/book_excerpt.asp?bookid=1570">this</a> page:
One approach was to use another difunctional peroxide that those already in use (hydrogen and adipoyl peroxides were already patented). I looked at some texts and noted one could make an aldol peroxide from formaldehyde and hydrogen peroxide. I put together some concentration variations of butadiene, isopropanol, formaldehyde, and hydrogen peroxide, to make the initiator in- situ. We set them up in the standard sealed polymerization bottles at 75 degrees Centigrade. Nothing happened for about two hours, and I looked in one them hourly. Just after the 2nd hour inspection, I went back to my desk for coffee, and one of the technicians raced up saying "Did you hear the explosion?". I hadn't, but went with him to the polymerization lab external door just in time to hear another one "cook off".
The lab was cleared of all personnel already, and one just barely missed being inundated by the 75 degree water as the first explosion went off. I put on face mask and rubber apron and crawled into the lab to turn off the steam and fill the bath with cold water. The lab floor was littered with sand sized glass particles, and one of the polymerization bottle guards was about 15 feet from the polymerization bath. After about a half hour of cooling, I donned apron, long gloves and face mask, and took out all the remaining bottles, and emptied those that still were intact- not many. The force of the explosion ripped the stainless caps off some of the bottle shields, and one of those shields remains on my desk to remind me I'm fallible.
This was the last day before my vacation was to start, so when I left after cleaning up, I was gone for at least a week. When I got back, I found that there had been an inquiry. Gerd Lenke had been assigned top look into the matter, and he found an ancient Gmelian book set which showed details of the formaldehyde/hydrogen peroxide products. The one I wanted (and probably got) was dimethylol peroxide, which melts about 60 degrees C, and is a "brisant" explosive at 72 degrees. It would not have detonated at 70 degrees, but I was five degrees higher. I still think it would be a good di-functional initiator, BUT...Handle With Care!

KABOOOM(pyrojustforfun) - 16-3-2003 at 19:02

Quote:

HEMEX group (High Energetic Material EXplosive) was studying DNU and they attempted the reaction with CH2=O... you get instantaneous polymerisation and precipitation of ureaformol polymer...the polymer didn't seem to have any inflamability or explosive properties!

we don't wanna react DNU with formaldehyde or its peroxide. DNU hydrolyses completely when is added to water

Quote:

Urea complexate H2O2 to make NH2-CO-NH2.H2O2

there is no urea in solution

Quote:

CH2=O doesn't survive long H2O2 in strong acidic media!

Quote:

NH2-NO2 self oxydate fast into N2O and H2O!

formaldehyde and its peroxide are just intermediates. their presence (even for a short time) is enough. otherwise HMTD or TMDD couldn't be made with the usual method, so is nitramide. it's unstable too but exists in solution (have ya read that PDF on lagen's site?)
Conclusion: there is still the chance that the explosive can be synthesized. if not, not for those reasons.
I haven't tried it yet because the last time I lost conc H2SO4 I couldn't get any afterwards. and I'm just too busy to concentrate battery acid(takes a long time)

PHILOU Zrealone - 24-3-2003 at 07:24

What I wrote were no objections to your post!

But now this is:
DNU stays in solution as long as NH2-NO2; their stability is about equal and before all DNU has been hydrolised to NH2-NO2; NH2-NO2 starts to decompose! Thus you will react a mix of DNU, Nitramide, formol peroxyde, formol and H2O2!

Normally amines, nitramines and CH2=O react by creating R-N=CH2 or R-NH-CH2OH or R-N(CH2OH)2
Then H2O2 peroxydase those!

HO-CH2-OOH might be part of the process but HO-CH2-O-O-CH2-OH seems rather unlikely to be part of it!

Proof of this is that HMTD is made from hexamine and H2O2 or from NH3/CH2=O/H2O2; I never saw any reference using a premix of CH2=O and H2O2 allowed to react at 60°C to form HO-CH2-O-O-CH2-OH and then react this with NH3!!!!

KABOOOM(pyrojustforfun) - 24-3-2003 at 19:20

lol I knew that. sorry if I seemed rude.
the problem with DNU may be solved if we replace it with O2N-NH-C=O-OCH2CH3. do u have info on it? (eg how it's made)
a file on Swedish Infomania said DHMP reacts with NH3 but it could be wrong.

more to discuss!

KABOOOM(pyrojustforfun) - 24-3-2003 at 19:50

what about a NH2OH CH2O H2O2 or a H2N-NH2 CH2O H2O2 system? the second one is harder or impossible as conc H2O2 and hydrazine react explosively.

PHILOU Zrealone - 25-3-2003 at 03:23

DNU is not a real problem because it will make side products but those may continue hydrolise and it would be as if you had plain NH2-NO2!

Carbamic ester are used to synthetise dinitramides!
RO-CO-NH2 + HNO3/Ac2O --> RO-CO +RO-CO-NH-NO2 and RO-CO-N(NO2)2
RO-CO-NH-NO2 -NaOH-> ROH + CO2 + NaNH-NO2
RO-CO-N(NO2)2 -NaOH-> ROH + CO2 + NaN(NO2)2

Virtually all amino groups that interacts with CH2(OH)2 are potential peroxydes makers!
But remeber that the molar ratios are important here!A different molar ratio will end up to give something else!

Such groups are:
H-NH2 (HMTD-hexamethylene triperoxyde diamine)
HO-NH2
NH2-NH2 (TTTD-1,2,7,8-Tetraaza-4,5,10,11-tetraoxa[6.4.1.12,7]tetradecane)
CH3-NH2
NH2-CO-NH2 (TMDD-Tetramethylene diperoxyde dicarbamide)
CH3-O2C-NH2

Maybe (?)
O2N-NH2
CH3-NH-NO2
NC-NH2
????

HMTD = C6H12N2O6
TTTD = C6H12N4O4
TMDD = C6H10N4O6

The molar ratio effect:
If you take a simple example of let say CH3-NH2 and CH2=O/H2O2:
if we have 1/1 for amine/formol,
You may expect:
CH2=O + H2N-CH3 --> HO-CH2-NH-CH3 and CH2=N-CH3
CH2=N-CH3 will lead reversibely to trimeric 1,3,5 triaza-1,3,5 trimethyl cyclohexane!
CH2=N-CH3 will add to a H2O2 molecule to get HOO-CH2-NH-CH3
From this you see that possible scenarios are:
CH3-NH-CH2-O-O-CH2-NH-CH3 and its condensation products with CH2=N-CH3...
CH3-NH-CH2-O-O-CH2-N(-CH3)-CH2-NH-CH3
CH3-NH-CH2-(CH3-)N-CH2-O-O-CH2-N(-CH3)-CH2-NH-CH3
Then finally after rearrangements you may get:
CH2(-(CH3-)N-CH2-O-O-CH2-N(CH3)-)2CH2
The two major products will be (CH3-NH-CH2-O-)2 and CH2(-(CH3-)N-CH2-O-O-CH2-N(CH3)-)2CH2 + polymers of the last one
Formula C4H12N2O2 and C10H24N4O4 that respects relatively well the ratio CH3-NH2/CH2O 1/1!
(C5H12N2O2)x

If we have a 1/2 molar ratio thus formol is in readily available even after first step reaction;
CH3-NH2 + CH2=O --> CH3-N=CH2
CH3-N=CH2 + CH2=O -H2O-> CH3-N(CH2OH)2
H2O2 + CH2=O --> HO-CH2-OOH
CH3-N=CH2 + HO-CH2-OOH --> CH3-N(CH2OH)(CH2OOH) (major product)
Then polymerisation of this will occure:
2CH3-N(CH2OH)(CH2OOH) --> CH3-N(CH2-O-O-CH2)2N-CH3 (cyclic dimer) and linear polymer (CH3-N(CH2-O-)2)x

We thus have now C6H14N2O4 (C3H7NO2)x

Molar ratio 1/1 provided (C5H12N2O2)x
Molar ratio 1/2 provided (C3H7NO2)x
Thus you get better peroxydation (better OB) from higher CH2=O content!!!

Of course the complexity of this kind of reactions goes up with the number of available H on the nitrogen!
NH3 > CH3-NH2> (CH3)2NH
NH2-NH2 > NH3

With hydrazine you may expect a lot of different compounds depending on the ratios!
NH2-NH2 -CH2=O->
1/1 ratio:
NH2-NH-CH2-OH and NH2-N=CH2
1/2 ratio:
NH2-N(CH2-OH)2 and HO-CH2-NH-NH-CH2-OH and HO-CH2-NH-N=CH2 and CH2=N-N=CH2
1/3 ratio:
HO-CH2-NH-N(CH2-OH)2 and CH2=N-N(CH2-OH)2
1/4 ratio:
(HO-CH2)2N-N(CH2-OH)2

Of course seeing this and regarding what I have explained from the CH3-NH2/CH2=O example you very soon conclude that
It must be possible to replace all H of the nitrogen by a -CH2-O- and make ring closure with those!

You then must expect the best peroxides to be with a slight excess of H2O2 vs stoechiometry:
(N(CH2-O-)3)x from NH3/3CH2O x=2 exist
(HO-N(CH2-O-)2)x from HONH2/2CH2O
((-O-CH2-)2N-N(-CH2-O-)2)x from N2H4/4CH2O
(CH3-N(CH2-O-)2)x from CH3-NH2/2CH2O
(O=C(-N(CH2-O-)2)2)x from (NH2)2CO/4CH2O
(CH3-O2C-N(CH2-O-)2)x from CH3-O2C-NH2/2CH2O

and Maybe
(O2N-N(CH2-O-)2)x from NH2-NO2/2CH2O
(CH3-N(NO2)-CH2-O-)2 from CH3-NHNO2/CH2O
(NC-N(CH2-O-)2)x from NC-NH2/2CH2O