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hissingnoise
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| Quote: | | Maybe it was Harris Tweed? |
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Laboratory of Liptakov
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You, all experienced chemists, too bad your time for answered for Octonitrocubane. He writes nonsenses. Registered 17. 3. 2016, first and only post
25. 3. 2016....
[Edited on 25-3-2016 by Laboratory of Liptakov]
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DubaiAmateurRocketry
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Dany's post from 2013 on nitrated-cyclodextrine, this contains all information you need
Link:
http://www.sciencemadness.org/talk/viewthread.php?tid=25823#...
2 years ago, I theorized on another forum of Cl-20 being caged into the cavity of cyclodextrine and its nitrated form. ( it is in another language,
the original paper theorized it could reduce the impact sensitivity of certain compounds):
Link:
http://tieba.baidu.com/p/2993864161
and guess what, this thing actually got synthesized recently on a paper published on CEJEM 
Direct link:
http://www.wydawnictwa.ipo.waw.pl/cejem/Vol-13-Number-1-2016...
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MineMan
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Interesting, does this look like a synthesis an amateur could follow??
From previous research my understanding was 1gram of CL-20 would be $10 to produce...
Does this paper show a more economic alternative...? I am hoping it is finally time for HMX to step aside!!
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Microtek
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On an amateur basis, CL-20 has proven to be very elusive. There are a few routes that seem like they could lead somewhere (condensation of
1,4-diformyl-2,3,5,6-tetrahydroxypiperazine with 1,1,2,2-tetranitraminoethane, or some routes using sulfaminates), but despite how promising they look
on paper, they haven't yet taken off.
I wrote my thesis on this topic (among others). It was inconclusive in the end.
IMO, ionic energetic materials are a much more promising way for the amateur to achieve performance in excess of what HMX can give.
I have been experimenting with some of the new materials (aminonitroguanidinium nitrate and the bis(triaminoguanidinium) salt of
bis(dinitroethyl)nitramine, though I'm not quite done with the latter).
Aminonitroguanidinium nitrate is easy to synthesize and crystallizes in very well-defined crystals, however they change over time in the open,
possibly due to loss of nitric acid (only a hypothesis based on the low basicity of aminonitroguanidine - I need to investigate a little more
thoroughly).
[Edited on 19-5-2016 by Microtek]
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Laboratory of Liptakov
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I cant a find data about amino nitroguanidine. It is nitroguanidine? Easy prepare you says? Hmm... And VoD? Thanks for answer...:-) Dr.
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kratomiter
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I'm also interested in the synthesis of aminonitroguanidine. I'm gonna try the synthesis of guanidine perchlorate and dinitroguanidine, but perhaps
aminonitroguanidine nitrate is more interesting. Is a secondary, right?
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DubaiAmateurRocketry
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That compound is infact one of my favorite energetic material. Synthesized by Prof.Klapotke in 2012.
The synthesis is far less exotic than some of the other energetic materials. All you need is nitroguanidine, easily found, and hydrazine
The hydrazinolysis of nitroguanidine results in 1-amino-3-nitroguanidine, (ANQ)
ANQ nitrate has a density of 1.91, very high considering how many gas it produces, and a VoD of 9550 m/s ! Also very high. This compound also has a
perfect OB. The sensitivity of ANQ nitrate is 10 J.
reference
Thomas M. Klapötke et.al, (2014) :1-Amino-3-nitroguanidine (ANQ) in High-performance Ionic Energetic Materials
Zeitschrift für Naturforschung B. Volume 67, Issue 6, Pages 573–588, ISSN (Online) 1865-7117, ISSN (Print) 0932-0776, DOI: 10.5560/znb.2012-0066
Direct link:
http://www.degruyter.com/view/j/znb.2012.67.issue-6/znb.2012...
Edit:
Corrected VoD from 9950 to 9550. Typo
[Edited on 20-5-2016 by DubaiAmateurRocketry]
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PHILOU Zrealone
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Theorically hydrazinolyse of nitroguanidine could lead to 2 compound depending on the amount of N2H4...
Just like guanidine may form aminoguanidine, diaminoguanidine and triaminoguanidine...
So here:
1°) (H2N-)2C=N-NO2 + H2N-NH2 --> H2N-NH-C(-NH2)=N-NO2 + NH3 (g)
Aminonitroguanidine (ANG)
2°) H2N-NH-C(-NH2)=N-NO2 + H2N-NH2 --> (H2N-NH-)2C=N-NO2 + NH3 (g)
Diaminonitroguanidine (DANG)
The later would be even more promising because it could be protonated twice
--> diaminonitroguanidine dinitrate, diperchlorate, dinitroformiate, bis-dinitramide
DANGDN
DANGDP
DANGDNF
DANGBDN
Also not to neglect the fact the initial compound (ANG) is basic...then it must be able to form transition metal complexes of oxoanions
(nitroformiate, chlorate, nitrate, perchlorate, and maybe bromate, iodate, perbromate, periodate) with energetic properties.
Maybe copper is too oxydant but Zn, Cd, Co, Ni, ... might do...
-->for example Ni(II) nitrate --> Ni(NO3)2. 6 ANG (if ANG monodentate) , Ni(NO3)2 . 3 ANG (if ANG bidentate), Ni(NO3)2 . 2 ANG (if ANG
tridentate).
Same of course would apply for DANG but here the dentition of the complexes might be more complex (without willing to make a bad word play  ) -->
polymeric complexes?
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
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DubaiAmateurRocketry
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Quote: Originally posted by PHILOU Zrealone  |
Same of course would apply for DANG but here the dentition of the complexes might be more complex (without willing to make a bad word play ) -->
polymeric complexes? |
haha, I wish that was the case, but let me give you a sad news:
I am not sure why, but guanidine in abbreviation is denoted by Q
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Microtek
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The reason for the choice of acronym is probably that abbreviating nitroguanidine as NG would lead to confusion (with nitroglycerine), especially
since both are used regularly in formulations of smokeless powder.
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kratomiter
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Wow, synthesis of DNQ seem pretty easy and straightforward for an amateur. I have some nitroguanidine waiting for hydrazinolysis right now
The yield is pretty low (45%), but its isolation is easy because it isn't water soluble. I'll try it this weekend.
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PHILOU Zrealone
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| Quote: Originally posted by DubaiAmateurRocketry | | Quote: Originally posted by PHILOU Zrealone |
Same of course would apply for DANG but here the dentition of the complexes might be more complex (without willing to make a bad word play ) -->
polymeric complexes? |
haha, I wish that was the case, but let me give you a sad news:
I am not sure why, but guanidine in abbreviation is denoted by Q |
A simple letter paradox is not a sad news...
ANQ or ANG; DANQ or DANG... Who really cares as long as we know what we are talking about...reason why I wrote the complete name aside (I try to do
that (and it is a good reflex for every user of SMF I think) everytime I use accronyms)
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
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PHILOU Zrealone
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| Quote: Originally posted by kratomiter | Wow, synthesis of DNQ seem pretty easy and straightforward for an amateur. I have some nitroguanidine waiting for hydrazinolysis right now
The yield is pretty low (45%), but its isolation is easy because it isn't water soluble. I'll try it this weekend. |
By DNQ, because you wrote hydrazinolysis, did you meant ANQ (ANG aminonitroguanidine), DANQ (DANG diaminonitroguanidine) or really DNQ
(dinitroguanidine)?
DNQ is (O2N-N=C(-NH2)-NH-NO2)
ANQ is (O2N-N=C(-NH2)-NH-NH2)
DANQ is (O2N-N=C(-NH-NH2)-NH-NH2)
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
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PHILOU Zrealone
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| Quote: Originally posted by PHILOU Zrealone | Theorically hydrazinolyse of nitroguanidine could lead to 2 compound depending on the amount of N2H4...
Just like guanidine may form aminoguanidine, diaminoguanidine and triaminoguanidine...
So here:
1°) (H2N-)2C=N-NO2 + H2N-NH2 --> H2N-NH-C(-NH2)=N-NO2 + NH3 (g)
Aminonitroguanidine (ANG)
2°) H2N-NH-C(-NH2)=N-NO2 + H2N-NH2 --> (H2N-NH-)2C=N-NO2 + NH3 (g)
Diaminonitroguanidine (DANG)
The later would be even more promising because it could be protonated twice
--> diaminonitroguanidine dinitrate, diperchlorate, dinitroformiate, bis-dinitramide
DANGDN
DANGDP
DANGDNF
DANGBDN
Also not to neglect the fact the initial compound (ANG) is basic...then it must be able to form transition metal complexes of oxoanions
(nitroformiate, chlorate, nitrate, perchlorate, and maybe bromate, iodate, perbromate, periodate) with energetic properties.
Maybe copper is too oxydant but Zn, Cd, Co, Ni, ... might do...
-->for example Ni(II) nitrate --> Ni(NO3)2. 6 ANG (if ANG monodentate) , Ni(NO3)2 . 3 ANG (if ANG bidentate), Ni(NO3)2 . 2 ANG (if ANG
tridentate).
Same of course would apply for DANG but here the dentition of the complexes might be more complex (without willing to make a bad word play ) -->
polymeric complexes? |
To add up more complexity 
There are also other interesting compounds that may form:
3°) Because the amino group of ANG may react on another molecule of NQ
2 (H2N-)2C=N-NO2 + H2N-NH2 --> O2N-N=C(-NH2)-NH-NH-C(-NH2)=N-NO2 + 2 NH3 (g)
--> N3,N3'-bisnitroguanidine (or N1,N2-bis-nitroformamidin-hydrazine (BNFAH) or 2,5-bis-nitroimino-1,3,4,6-tetraaza-hexane (BNITAH))
The later may be oxydised to a diazo compound
O2N-N=C(-NH2)-NH-NH-C(-NH2)=N-NO2 -ox-> O2N-N=C(-NH2)-N=N-C(-NH2)=N-NO2 + H2O
-->N1,N2-bis-nitroformamidin-diazene (BNFADA) or 2,5-bis-nitroimino-1,3,4,6-tetraaza-hex-3-ene (BNITAHE)
4°) Because the amino group of DANG may react on another molecule of ANG or of DANG
H2N-NH-C(=N-NO2)-NH-NH2 + H2N-C(=N-NO2)-NH-NH2 --> H2N-NH-C(=N-NO2)-NH-NH-C(=N-NO2)-NH-NH2 + NH3 (g)
--> 3,6-bis-nitroimino-1,2,4,5,7,8-hexaaza-octane (BNIHAO)
The later may be oxydised to a diazo compound
H2N-NH-C(=N-NO2)-NH-NH-C(=N-NO2)-NH-NH2 -ox-> H2N-NH-C(=N-NO2)-N=N-C(=N-NO2)-NH-NH2 + H2O
---> 3,6-bis-nitroimino-1,2,4,5,7,8-hexaaza-oct-4-ene (BNIHAOE)
5°) ANG may also react with itself leading to a cyclic tetrazane
O2N-N=C(-NH2)-NH-NH2 + H2N-NH-C(-NH2)=N-NO2 --> O2N-N=C(-NH-NH-)2C=N-NO2 + 2 NH3(g)
--> 3,6-bis-nitroimino-1,2,4,5-tetraazacyclohexane (BNITACH)
The later by virtue of resonance (nitroimino - nitramino) and oxydability of the hydrazine moeities will probably turn into a cyclic tetrazine
O2N-N=C(-NH-NH-)2C=N-NO2 -ox-> O2N-NH-C(N4)C-NH-NO2 + H2O
--> 3,6-bis-nitramino-1,2,4,5-tetraazabenzene (BNITAB) or 3,6-bis-nitramino-1,2,4,5-tetrazine (BNITaz)
It may prove to be very unstable and easily hydrolysable because nitramine on highly electron withdrawing aromatic rings tends to split off NO2 as
nitronium.
O2N-NH-C(N4)C-NH-NO2 + 2 H2O --> H2N-C(N4)C-NH2. 2 HNO3
--> diaminotetrazine dinitrate
(O2N-NH-C(N4)C-NH-NO2 --> (-)NH-C(N4)C-NH(-) + 2 NO2(+))
(2 H2O + 2 NO2(+) --> 2 H(+) + 2 HO-NO2)
((-)NH-C(N4)C-NH(-) + 2 H(+) --> H2N-C(N4)C-NH2)
The nitraminos will be very acidic and may form interesting salts but this should be done without water.
6°) There is also the possibility of chain formation in a polymeric fashion
(-C(=N-NO2)-NH-NH-)n and oxydation products like (-C(=N-NO2)-N=N-)n
All those compounds may, just like 1°) and 2°) should, allow for complexation with transition metal complexes of oxoanions (nitroformiate, chlorate,
nitrate, perchlorate, and maybe bromate, iodate, perbromate, periodate) with energetic properties.
[Edited on 20-5-2016 by PHILOU Zrealone]
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
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Microtek
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Klapötke et al discuss the mechanisms involved in the formation of ANQ and some of the others that Philou speculate on. It seems that DANQ is too
unstable to be isolated from this medium, since adding more hydrazine simply results in a reduced yield of ANQ.
I include the full paper here, so everyone can see for themselves:
Attachment: Aminonitroguanidine nitrate.pdf (3.9MB)
This file has been downloaded 781 times
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PHILOU Zrealone
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| Quote: Originally posted by Microtek | Klapötke et al discuss the mechanisms involved in the formation of ANQ and some of the others that Philou speculate on. It seems that DANQ is too
unstable to be isolated from this medium, since adding more hydrazine simply results in a reduced yield of ANQ.
I include the full paper here, so everyone can see for themselves: |
Interesting paper. Thank you.
In the paper they explain that hydrazinolysis may go through 2 ways...
1) Substitution of the NH2
(H2N-)2C=N-NO2 + H2N-NH2 --> H2N-NH-C(-NH2)=N-NO2 + NH3(g)
This process of formation of ANG is not favourised because they only got 45% yield while 2 NH2 are available over 1 N-NO2...statistically one would
then expect 66% yield.
2) Substitution of the =N-NO2
(H2N-)2C=N-NO2 + H2N-NH2 --> (H2N-)2C=N-NH2 + H2N-NO2
The later amino guanidine (AG) may react further to diamino guanidine (DAG) and triamino guanidine (TAG)
Part of the aminonitroguanidine in 1) may also react with excess hydrazine to DANG, DAG and TAG.
I suspect DANG would have more chance to be done in workable quantities if working from ANG and no exces N2H4!
[Edited on 21-5-2016 by PHILOU Zrealone]
PH Z (PHILOU Zrealone)
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Microtek
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According to a paper by Castillo-Melendez and Golding, the yield of ANQ can be as high as 60% given the right reaction conditions (55 C, 15 minutes
reaction time). The paper is from 2004, so it's older than the one I posted by Klapötke, et al. This could indicate that it is quite difficult to
reach those numbers. I think this is supported by the fact that the yield peak is quite narrow.
Attachment: Amino-nitroguanidine prep 2004.pdf (428kB)
This file has been downloaded 720 times
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glymes
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Would 5-aminotetrazole be basic enough to form 5-aminotetrazole perchlorate? It'd either work and be a fantastic oxidiser or there wouldn't be a
reaction.
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PHILOU Zrealone
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| Quote: Originally posted by glymes | | Would 5-aminotetrazole be basic enough to form 5-aminotetrazole perchlorate? It'd either work and be a fantastic oxidiser or there wouldn't be a
reaction. |
With a pKa of 6.0 it is a weak acid in the range of H2CO3... so with a pKa of -8 HClO4 is 1014 times more acidic.
--> 5-ATz will indeed form a perchlorate.
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
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glymes
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Oh right... That rather changes things up!
So would it be [(C-NH2)-N3-NH]ClO4? The OB looks good. Indeed, would it be able to form nitroformate salts? I feel an investigation coming on....
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kratomiter
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It was a mistake, I mean ANQ nitrate. I'll post results tomorrow if I get something interesting.
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glymes
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Right.
Perdifluoroaminohexamethyenetetramine. C6N16F24 --> 6CF4 + 8N2.
C6N4H12 + 12N-bromosuccinide --> C6N4Br12 + succinide
C6N4Br12 + 12HNF2 --> C6N16F24
Bromine is generally a good leaving group. For the sake, call it PDF HMTA, as I'd rather make it sound like a photocopier than a mouth orgy.
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DubaiAmateurRocketry
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| Quote: Originally posted by glymes | Oh right... That rather changes things up!
So would it be [(C-NH2)-N3-NH]ClO4? The OB looks good. Indeed, would it be able to form nitroformate salts? I feel an investigation coming on....
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It would be a decent oxidizer, however not good enough.
I personally do not like to introduce carbon atoms in the anion because they increase the overall average molecular weight of the exhaust in a
propellant.
If you take a look at the ANQ-dinitramide-monohydrate, it is very stable, has a VoD of nearly 9200, produces more gas than ANQ-Nitrate.
However if you put a nitroformate in there, the gas produced, L/kg will be significantly lower.
Edit:
Anyone have any idea if the ANQ-Dinitramide-monohydrate could be turned into... maybe ANQ-Dinitramide-monohydroxylamide ?
[Edited on 21-5-2016 by DubaiAmateurRocketry]
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glymes
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Hold up.
Where on earth are you fitting the dinitramide groups, as ANQ is NO2-(C=NH)-NH2? Would it just be [NO2(C=NH2)-NH2]- 2[NO2-N-NO2]+ or something like
that?
If that works, forming NO2CNHNH2(NO2-N-NO2]2 * H2O I see no reason why HO-NH2 should not be able to kick the H2O out and form NO2CNHNH2(NO2NNO2)2 *
HONH2
More neatly:
CH3N3O2 + NH3N3O4 --> CH3N6O6 + NH3
CH3N6O6 + H3NO --> C3H6N7O7
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