Sciencemadness Discussion Board

Tetramethylenehexaamine

ptit nouveau - 8-2-2005 at 11:45

C4H12N6 is a dougle hexagone with two trivalent nitrogen, the 4 next coins are methylene (CH2) ans the 4 other coins are secondary amine (NH). He can be make by reaction between formol and hydrazine ( 4H2C=O + 3H2N-NH2 ---> C4H12N6 + 4H20). What energetical meterials can be make with this compoud? How H+ can-he accept (2? 4? 6?)? I think he can be use to make very powerful substance. Sorry for my English (I'm French).

JohnWW - 8-2-2005 at 13:48

An amine can in theory accept as many H+ ions as it has basic N atoms. However, if the N atoms are in fact neighboring, as in hydrazine derivatives, there may well be some question about the stability of the amine salt. As for making this polybasic amine into an explosive compound, the best way would be to react it with the maximum possible amount of either HNO3 or HClO4, to form a nitrate or perchlorate.

artem - 8-2-2005 at 22:56

FA(formalazine) and TFTA (C4H12N6) were discussed as a fuel for rocket engines. Some information about nitrate of the product of the N2H4+CH2O - condensation is in the article (PEP 1986, 6). The subj is explosive (>TNT); structure is unknown.

Microtek - 9-2-2005 at 07:00

I was leafing through the journal of heterocyclic chemistry today ( looking for tetrazoles ) when I came across some condensation products of hydrazine and formaldehyde. IIRC the product was shown as two fused six-membered rings having two bridgehead nitrogens and then another two nitrogens opposite the bridgeheads in each ring.
There was also mentioned the condensation product of hydrazine hydrate with formaldehyde and hydrogen peroxide; a fused ring system of two seven-membered rings and a central maximally symmetric six-membered ring with 4 nitrogens. The two seven-membered rings have a peroxy moeity like this: -O-CH2-N-CH2-N-CH2-O- join the two oxygens.
The two nitrogens are part or the central ring.

If anyone is interested, I think it was in Vol 38 issue 3.

chemoleo - 9-2-2005 at 07:05

Quote:
Originally posted by Microtek
There was also mentioned the condensation product of hydrazine hydrate with formaldehyde and hydrogen peroxide; a fused ring system of two seven-membered rings and a central maximally symmetric six-membered ring with 4 nitrogens. The two seven-membered rings have a peroxy moeity like this: -O-CH2-N-CH2-N-CH2-O- join the two oxygens.
The two nitrogens are part or the central ring.

If anyone is interested, I think it was in Vol 38 issue 3.


I think this peroxide was already discussed, in the amine peroxide thread, although the structure you describe seems somewhat different?!?

[Edited on 9-2-2005 by chemoleo]

Axt - 9-2-2005 at 07:25

Quote:
although the structure you describe seems somewhat different?!?


Though the same empirical formula, this (presumably) latter reference, if right, may explain why its tetraperoxide (thus possessing simular structure of HMTD) is not possible. Any chance of you providing the reference Microtek?


[Edited on 9-2-2005 by Axt]

artem - 9-2-2005 at 22:51

Quote:
Originally posted by Microtek
I was leafing through the journal of heterocyclic chemistry today ( looking for tetrazoles ) when I came across some condensation products of hydrazine and formaldehyde. IIRC the product was shown as two fused six-membered rings having two bridgehead nitrogens and then another two nitrogens opposite the bridgeheads in each ring...

There are at least three products with various spectra - above mentioned tetraformaltriazine, FA - polymer based on the 1.3-diazacyclobutane - rings, and the product, described in PEP (condensation of 2mole CH2O + 1mole N2H4, as for FA, but other conditions).

Microtek - 9-2-2005 at 23:24

It was:

2001 Volume 38, pp. 541-559
Annelated[1,2,4,5]Tetrazines
Ahmad S. Shawali, Said M. Elsheikh
Department of Chemistry, Faculty of Science, University of Cairo, Giza, Egypt


It was a review article and it contained quite a number of interesting reaction schemes.

ptit nouveau - 15-2-2005 at 04:51

What is the reaction of tetramethylenehexaamine with HNO3?

AngelEyes - 15-2-2005 at 08:38

Isn't it hexamethylenetetraamine (ie 6 methylene and 4 amine)...?

Type that name and 'nitric' into Google and see what hapens.

chemoleo - 15-2-2005 at 18:48

If you read the first post of this thread, HYDRAZINE is used as opposed to ammonia. That should answer your 'question'. Please read topics carefully before questioning things!!

artem - 29-3-2006 at 04:20

References for TETRAFORMALTRIAZINE (TFTA) and FORMALAZINE (FA)
US3664131:TFTA basically can be formed by reacting an aqueous solution of formaldehyde and hydrazine at room temperature. The solution is allowed to stand several days, the TFTA separates as white needles which can be readily recovered. The synthesis of TFTA is reported in the following literature references: R. Stole, BER 40, 1,505, (1907) and K. Hauffman and D. Storm, BER 45, 1,728, (1912).
Example: 487 grams of a 37 percent solution of formaldehyde in water was added dropwise to 200 grams of a 75 percent solution of hydrazine in water over a period of 4 1/2 hours. The reaction mixture was kept at 50C. Solid TFTA separated upon cooling of the mixture.
The melting point of TFTA is 245C. d~1.3g/cm3, ΔH=+351+/-6 KJ/mole
Impact sensitivity experiments indicate that TFTA is substantially less sensitive to impact than TAZ or THA.
РЕР 1985,10, 39:
TFTA, synthesis: Mitsuo Mashima, Bull.Chem.Soc.Japan, 39, 504, 1966
White solid, melting 183C (DTA) with decomposition (yellowish liquid). DTA, onset: 145С, -50%mass 220С.
FA, synthesis reference: J.F.Walker, "Formaldehyde", 3-rd ed.,Reinhold Publishing Company, NY 1964, p.239.
White amorph., DTA exotherm 246C, peak~258C, -50%(air) 270С.

РЕР 1986, 6:
Mixing 2mole formaldehyde (water solution) and 1mole hydrazine (cooling) gives polymer, IR spectrum differs from FA. It easily dissolves in NA without decomposition, after cooling precipitate forms.
The precipitate has two DTA-exotherms (100 and 230C), the sensitivity was substantially less than PETN. It was detonating by blasting cup 6, VoD(0.8g/cm3, tube 25mm) = 4375m/s, lead block expansion 430ml(PETN 512ml)

There is also another reference for (CH2O+N2H4) condensation: N.P.Neureiter, J.Am.Chem.Soc. 81, 2910 (1959).

When I was trying to modify the synthesis of “trimethyleneazine peroxide” in order to prepare it by the reaction of (CH2O+N2H4)+H2O2, there was a problem: if formaldehyde was added to hydrazine hydrate, clear solution suddenly gave the precipitate at the ratio CH2O/N2H4 ~1..1.5, and when hydrazine was dropped to formaldehyde, unsufficient cooling resulted in instantaneous exothermic reaction with solidifying all the mix (I think it was formed alpha-polyoxymethylene).

Boomer - 29-3-2006 at 23:34

"An amine can in theory accept as many H+ ions as it has basic N atoms"

That bugs me for some time: What determines how many HNO3 can be added? Why are there mono- and dinitrourea, but I never read about urea dinitrate. Why does hexamine only form a dinitrate, though all four N are identical? Could nitroguanidine dinitrate exist, with two .HNO3 on the outer amines, the one in the middle having the NO2? What limits this?

PHILOU Zrealone - 30-3-2006 at 09:50

Quote:
Originally posted by Boomer
"An amine can in theory accept as many H+ ions as it has basic N atoms"

That bugs me for some time: What determines how many HNO3 can be added? Why are there mono- and dinitrourea, but I never read about urea dinitrate. Why does hexamine only form a dinitrate, though all four N are identical? Could nitroguanidine dinitrate exist, with two .HNO3 on the outer amines, the one in the middle having the NO2? What limits this?


Molecular orbitals and the electronegativity of the vicinal atoms or atom groups...
The same story is involved in why -NO2 deactivates aromatic ring and increase acidity of phenolic group...

Actually hydrazine dinitrate and diperchlorate exists but are rather unstable and must be kept in strong HNO3 or HCLO4 media...otherwise they hydrolyse.
Owing to the corrosive and dangerous character of the acids and of the hydrazindium oxosalts...they were not further investigated. Too rich at oxygen and too reactive towards metals and organics...
I imagine that introducing electrodonnor substituents to hydrazine will help increasing basicity.
Tetramethylhydrazine> trimethyl-> sym dimethyl- > vic-dimethyl-> (Mono)methyl-> hydrazine.

Nick F - 30-3-2006 at 18:56

Look at DABCO (1,4-diazo[2.2.2]bicyclooctane), for example. pKaH of diprotonated DABCO is 3.0, that of monoprotonated DABCO is 8.8. The inductive effect makes the second proton almost a million times more acidic, even though the nitrogens are quite widely seperated!!

artem - 30-3-2006 at 21:27

Quote:
Originally posted by PHILOU Zrealone
Owing to the corrosive and dangerous character of the acids and of the hydrazindium oxosalts...they were not further investigated.

Hmm... And what about further publications? for example, PEP 2003-2 (Review. Thermal Decomposition of Energetic Materials 85: Cryogels of Nanoscale Hydrazinium Diperchlorate in Resorcinol-Formaldehyde)? HDP has the same order problems as HNF, but HNF is widely investigated now.

Madandcrazy - 4-4-2006 at 07:31

Nice threath about questions for sysntheses about multicyclic
chemicals. Contingently interested is to this, do all chemical reacting as well as, for instance by a nitration with HNO3 and the multicycle is broken and the (NO2 ...) group takes up to the nitrogen atom ?
Is it by a easy chemical than hexametylenediamin too ?

PHILOU Zrealone - 4-4-2006 at 08:05

Quote:
Originally posted by artem
Hmm... And what about further publications? for example, PEP 2003-2 (Review. Thermal Decomposition of Energetic Materials 85: Cryogels of Nanoscale Hydrazinium Diperchlorate in Resorcinol-Formaldehyde)? HDP has the same order problems as HNF, but HNF is widely investigated now.


Have you noticed the "cryogels and nanoscale" terms they use? This means low temperature and very tiny amounts.
HDP is very very acidic and oxydising.And for sure very hygroscopic.

I once made 50g of HP and it was a hell to get it dry...I had a batch of 70g of HN and the HP took all the moisture out of the HN.While drying it corroded all the metal pieces that were arround.

artem - 5-4-2006 at 20:07

Quote:
Originally posted by PHILOU Zrealone
Have you noticed the "cryogels and nanoscale" terms they use? This means low temperature and very tiny amounts.

This is hasty opinion. Cryogels technique is "freeze-drying or lyophilisation of sol-gel". That's why it is not very complex to use it in commercial scale.
Quote:
Originally posted by PHILOU Zrealone
HDP is very very acidic and oxydising.And for sure very hygroscopic.
I once made 50g of HP and it was a hell to get it dry...I had a batch of 70g of HN and the HP took all the moisture out of the HN.While drying it corroded all the metal pieces that were arround.

Yes, HDP is acidic. This requires special binding and curing agents.
As for "oxydising" - what do you mean?
ADN is very hygroscopic too, and it is more unstable, but it was used in rocket engines sucessfully in 70-th.
HP - is it mono- or di- perchlorate? What was the synthesis? And what was the application :) ?

PHILOU Zrealone - 6-4-2006 at 09:36

HP is hydrazine perchlorate and HDP is hydrazine diperchlorate.

Synthesis was simple!
1)NH2-NH3-OH (NH2-NH2.H2O or 80% hydrazine solution)
2)HClO4 (79%)
Were used and dilluted with distillated H2O to get arround 30% solutions.
It was put in the freezer en once freezing cold, both solutions were mixed. N2H4.HClO4 solution was obtained (it heats a lot!)

I had already under hand hydrazine nitrate and Ni(NH2-NH2)3(NO3)2
I wanted to test HP because it is powerful but also much more sensitive...to friction and impact....read detonable
This is true but you need it very dry or heated.
I had a kitchen detonation of 50mg of it while making a heatsensitivity test on it...it curved completely the incineration spoon I was holding...what a BANG. Spoon was lifted in the air at 3 meters high and spinning at incredible speed. Spoon had a U shape because it had twisted itself arroun my hand.There was a serious notch on the side of the spoon.
While making the test HP melted quite fast and inflamed without spectaular effect...then I tried with a lower flame and while trying to get the liquid stuf from my spoon on the hotplate...I hit slightly the spoon on the superheated surface...

Why did I study HP?
Strangely all perchlorates of amines outperform nitrates of the same amines ... but HP. So it is the little black duck and I stil dont understand why it is so VOD is lower than that of HN....
GP > GN (guanidine)
HDP > HDN (hexamethylenetetramine)
AP > AN (ammonium)
MAP > MAN (methylamine)
EDADP > EDADN (ethylendiamine)
...
but
HP < HN (hydrazine)

:mad::(:mad:

Maybe HAP > HAN? (hydroxylamine perchlorate vs nitrate?)

[Edited on 6-4-2006 by PHILOU Zrealone]

[Edited on 6-4-2006 by PHILOU Zrealone]

artem - 7-4-2006 at 11:53

Quote:
Originally posted by PHILOU Zrealone
Synthesis was simple!
1)NH2-NH3-OH (NH2-NH2.H2O or 80% hydrazine solution)
2)HClO4 (79%)
Were used and dilluted with distillated H2O to get arround 30% solutions.

I used ~56%HClO4 and 68%N2H4 without further diluting. And almost dry crystalls were formed next day (temperature ~30C, open saucer, ~30g).To dry HN from ~60%HNO3 it takes about 4days (the same conditions). So, I think HN is more hygroscopic. Why took your HP all the moisture out of the HN?
Dry HP tends to form N2H5ClO4*0.5H2O. It is formed below ~60C and it is not very hygroscopic, but it is not so for N2H5ClO4. Another reason may be the impurity of HDP, as HP formed low-melting eutectics with many salts, which became liquids with some percents of water.
By the way, the more simple way to produce HP is the evaporation of AP+N2H4*H2O mix.
Quote:
Originally posted by PHILOU Zrealone
I had a kitchen detonation of 50mg of it while making a heatsensitivity test on it...it curved completely the incineration spoon I was holding...what a BANG.

Unfortunately, pure dry HP is unpredictable subj. I cannot to initiate it by hammer, by friction and by ignition in small metal tubes, but it may be VERY dangerous, especially at elevated temperatures. I had unexpected detonation once (~100g).
That's why I prefer to use it in diluted state.
Quote:
Originally posted by PHILOU Zrealone

Strangely all perchlorates of amines outperform nitrates of the same amines ... but HP. So it is the little black duck and I stil dont understand why it is so VOD is lower than that of HN....
GP > GN (guanidine)
HDP > HDN (hexamethylenetetramine)
AP > AN (ammonium)
MAP > MAN (methylamine)
EDADP > EDADN (ethylendiamine)
...
but
HP < HN (hydrazine)

:mad::(:mad:

Maybe HAP > HAN? (hydroxylamine perchlorate vs nitrate?)

ClO4- is nore active and perchlorates are more detonable, and HP-HN also. HP detonates in plastic tubes ~2mm, HN >10-12mm. But the brisance, lead block expansion depend by Qexpl of these subjes also.
Most of perchlorates have good OB, good Qexpl and high density. But when you have positive OB, nitrates are close. HN>HP, and AN>AP also.
So, HAN>HAP.

Madandcrazy - 12-4-2006 at 07:37

Interested,

are some by-products ;) of a syntheses useful when a imin should be prepared and reacted with three other components.

example are
N(C2H6)3 triphenylimin ;)
or a
N-amino-furazan should be prepared.

Maybe a hydrazin components are useful for a iminbinding and some synthesis like this, but how reacted for instance the NH2-NH-(C6H11) group to NH2-N(C6H11)2.
Is it easy realizable when the group cyclohexylhydrazin is threated with chlorocyclohexan in the selected solvent and it should reacted to di(phenylcyclohexan)hydrazin NH2-N(C6H11)2. ?
It would give surely n,n´dicyclohexylhydrazin (C6H11)-NH-NH-(C6H11)

[Edited on 12-4-2006 by Madandcrazy]

[Edited on 4-23-2006 by Polverone]

the original PEP

artem - 2-6-2006 at 10:10



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