Sciencemadness Discussion Board - Dihydroxyacetone peroxide

Dihydroxyacetone peroxide

Adas - 16-12-2011 at 13:47

Hello SM,

This idea had been in my head for so long now, so I decided to share it and see your opinions about it.

I was thinking if something like DHAP (with structure similar to TATP) can be made. I can't find any references, but this is not impossible, I think. DHA is just PITA to get/synthesize.

I was also thinking about nitrating the -OH groups (before or after the peroxidation, not sure). The product may be more stable then, because electron-accepting groups increase stability of peroxide bond. Also it would have perfect OB.

What do you think? And is there any way to synthesize DHA easily?

AndersHoveland - 16-12-2011 at 14:57

Yes, I think an interesting peroxide explosive could be formed from dihydroxyacetone.
The problem, of course, would be obtaining or making the dihydroxyacetone.

The hydroxy groups could potentially be "peroxidated", for lack of a better word, through tautomerization.
HO-CH2-C(=O)-CH2-OH <==> HO-CH=C(-OH)-CH2-OH <==> O=CH-CH(-OH)-CH2-OH
This is indeed why hydroxyacetone so easily condenses with amines. It essentially can act as an aldehyde, rather than just a ketone.

For the possible dynamics of the chemistry of a very much related compound, see my site page:
https://sites.google.com/site/energeticchemical/dppp
I wanted to post this under the "Diphoronepentaperoxide (DPPP)" thread in this forum, but unfortunately that thread was closed.

Rosco Bodine - 16-12-2011 at 16:37

@AndersHoveland

DPPP was thoroughly and systematically, reliably tested many different ways and 100% debunked. Tests included solubility in toluene, sublimation of samples, critical diameter and FTIR.....all indicating "DPPP" is nothing else but impure TCAP.

Yet on your site you say:

Quote:

Some have even suggested that the alleged "DPPP" is only acetone peroxide, pointing to an MIR test done on a sample of "DPPP". This specific test, however, had several potential flaws, and the results should be viewed with skepticism.

You really should give it a rest with unscientific speculation. It is the unscientific speculations as you are given to making with uncanny regularity that is what deservedly ought to be viewed with skepticism. With too much of what you say
is a pseudoscientific yet at the same time "professorial" and tutorial tone ...while simultaneously there is often unreliable or incomplete or overreaching, or incorrect "information" in what you say. You can't teach what you simply don't know.

Adas - 17-12-2011 at 06:22

Merck-Chemicals sells pure DHA, for cosmetic purposes, but I am not sure if they sell to individuals/if the purchase is worth it. I have really no money to waste.

About DHAP: IMO, it is possible, that it forms higher polymers than TATP, because DHA itself is found as a dimeric form at certain conditions, so it can also have some effect on DHAP formation. And if DHAP can be nitrated, the -ONO2 groups may increase the peroxide bond stability for 2 reasons:

1. As I said before, electron-accepting groups are known to stabilise the peroxide bond
2. -ONO2 group requires some space, so it may also protect the peroxide bond from mechanical stimuli.

Ozone - 17-12-2011 at 06:56

DHA is the simplest keto-sugar, analogous to glyceraldehyde. It is a very fast Maillard browning reactant, which is why it is sold as the main ingredient in artificial tanning products--it reacts with the protein in the skin to make brown-stuff. It is not controlled, and is not too expensive. However, is is sold as the dimer, and must be cracked via distillation with a trace of acid prior to use.

The structure for the dimer is attached.

Cheers,

O3

Adas - 17-12-2011 at 07:28

Eww... I have no distillation apparatus. What a shame. Those things cost fortune!

killswitch - 18-12-2011 at 19:11

Quote: Originally posted by Rosco Bodine

@AndersHoveland

DPPP was thoroughly and systematically, reliably tested many different ways and 100% debunked. Tests included solubility in toluene, sublimation of samples, critical diameter and FTIR.....all indicating "DPPP" is nothing else but impure TCAP.

Yet on your site you say:

Quote:

Knock off the personal vendetta, Rosco. Trying to troll Anders never works, because he's a less bitter and hateful person than you.

Rosco Bodine - 19-12-2011 at 19:24

There is no personal vendetta or trolling going on here, nor any bitterness or hatefulness. Chemistry is a business which needs a certain candor, reserve, and accuracy about content. It is not a convention of tongue in cheek bullshitters where a contest is occurring to see the biggest technorapping bullshitter win first prize. Some folks don't know the difference when they are hearing rap instead of science. But it grates on some of our nerves. I had nothing to do with the bans that were put on the earlier interations / avatars of Anders for his personal version of overreaching theoretical "science" ....did not even complain.....
but certainly did notice. Knowing sure things in modest supply is better than knowing huge amounts of things that just aren't true, while having misplaced confidence in such illusions. Anders spams this forum with a link to bullshit about DPPP that had my name by inference as a source of allegedly "unreliable" information and I take exception. If you don't like that .....too bad.

Sedit - 19-12-2011 at 19:37

Killswitch I really hope you are an old member under a new name because if you really came here with 9 post and started telling RB to lay off AH then you know little about who is right and who may be wrong. Just think before you speak because IF you know nothing of either person then telling one to lay off personal vendettas just makes you look like yet another pseudonym of AH.... and those are getting old IMO.

Bot0nist - 19-12-2011 at 19:41

Quote: Originally posted by Sedit

you look like yet another pseudonym of AH.... and those are getting old IMO.

I had assumed this as well.

Adas - 20-12-2011 at 08:59

Okay guys, but try to get less off-topic now. This is starting to be personal. This is not anything I was asking for

Rosco Bodine - 20-12-2011 at 09:51

You were asking for information about a hypothetical or unknown reaction scenario and your first reply was a dubious answer. If only that much was better said, without further elaboration, then pardon me, it seemed unavoidable.

Ozone gave the best answer. You may want to look at reaction with formaldehyde as potentially interesting also, which may or may not lead to an intermediate of further usefulness.

In one reference, IIRC, gentle oxidation of glycerin by H2O2 using a ferrous sulfate catalyst will produce the glyceraldehyde. There are other methods, search and find.

[Edited on 20-12-2011 by Rosco Bodine]

franklyn - 22-12-2014 at 18:58

It always pays to search the forum first for past contributions before posting. The material cited heading this thread has possibilities not discussed thus far which have occurred to me since then. TATP is made of three molecules of Dimethyl ketone joined with Peroxo groups. Instead of Methyls , with Ethyl groups the reagent becomes Diethyl ketone which can also form a trimeric peroxide.

Diethyl Ketone Triperoxide, DEKTP
http://www.google.com/?gws_rd=ssl#q=Diethyl+Ketone+Triperoxi...
3,3,6,6,9,9-hexaethyl-1,2,4,5,7,8-hexaoxacyclononane
http://www.ncbi.nlm.nih.gov/pubmed/19893236
" stability of DEKTP is calculated 20-50 times greater than that of TATP "
http://webbook.nist.gov/cgi/inchi/InChI=1S/C15H30O6/c1-7-13(8-2)16-18-14(9-3,10-4)20-21-15(11-5,12-6)19-17-13/h7-12H2,1-6H3

Substituting the Methyls of Dimethyl ketone with Hydroxymethyl groups , the starting reagent is then :
Glycerone
Dihydroxyacetone
1,3-Dihydroxypropanone
http://www.google.com/?gws_rd=ssl#q=dihydroxyacetone

The observation that the two Hydroxyls might be substituted with Nitrate groups ( providing the ketone is not also oxidized in the process ) should yield something comparable to Glycol Dinitrate or Glyceryl Trinitrate.

The alternative prospect is to proceed ahead to make instead the peroxide trimer analogous to DEKTP
3,3,6,6,9,9-Hexahydroxymethyl-1,2,4,5,7,8-hexaoxacyclononane

What is particularly interesting about this is that the six Hydroxyl groups can then be substituted with Nitrate groups more readily since peroxides remain stable in acid media.
3,3,6,6,9,9-Hexanitratomethyl-1,2,4,5,7,8-hexaoxacyclononane

Given the mol weight and comparative size of this molecule , it's sure to have relatively high density. Having perfect oxygen balance , it should exhibit better performance than PETN although sensitivity may be somewhat greater.

{(-C(CH2NO3)2(OO-)}3 => 9 CO2 + 6 H2O + 3 N2

Many known Organic peroxides are listed here _
http://www.sciencemadness.org/talk/viewthread.php?tid=16362#...

.

deltaH - 22-12-2014 at 22:59

Franklyn, by a strange coincidence I too was considering exactly the same thing not two days ago! Yes, the hexanitrate looks very interesting indeed what with it's perfect OB and all.

I think though that the presence of the hydroxyls introduces two challenges:

(A) Dihydroxyacetone being the simplest ketose, can isomerise to glyceraldehyde under acidic conditions. Indeed, the oxidation of glycerine with hydrogen peroxide and a ferrous salt produces a mixture of both.

(B) The cyclic peroxide of dihydroxyacetone would probably be very soluble being a polyol. This might hamper yields in a peroxidation as an equilibrium with its hydrolysis in solution may be limiting, i.e. this type of equilibrium:

-R-O-O- + H2O <=> R=O + H2O2

So I think IMHO, the ketone being peroxidated should preferably lack hydrophilicity in it's adjacent groups.

Perhaps the hypothetical way to go is to first react dihydroacetone with an excess of acetone and sulfuric acid catalyst to form the protected molecule DMDO then peroxidate, followed by further reactions... :

[Edited on 23-12-2014 by deltaH]

PHILOU Zrealone - 23-12-2014 at 05:28

Dihydroxyaceton is not nitratable directly because it is a strong reductor due to an equilibrium with 2,3-dihydroxy-propanal...
It has the ability to polymerize into dark polyphenolic stuffs (see its use as artificial suntanner).

Just as aceton (propanone) is unstable towards HNO3, so would DHA.
A mix of aceton and HNO3 usually ends up (in less than a minute) by boiling out nitrous fumes and runnaway, splashing all the beaker contain arround.

It could be nitrated by a derivated way via war gas lacrymator dichloroaceton and reaction with silver nitrate saturated solution...
Cl-CH2-CO-CH2-Cl + 2 AgNO3 --> O2N-O-CH2-CO-CH2-O-NO2 + 2 AgCl (s)

The halocetons are highly reactive towards substitution due to ceton group activation much more than allylic halide or benzylic halide...

The resulting dinitrate molecule will be very powerful explosive but might suffer hydrolysis behavior (and unstability-explosive runaway) because of the cetonic group and enol-ceton equilibrium what favors hydrolysis and set HNO3 free. This effect is seen in nitrosuggars (nitrate esters of suggars - nitrohydren) what are reputed unsafe to store.
Probably owing to some hydrolysis, the free HNO3 oxydizing the aldehyd group into carboxylic acid with self heating and runaway.
O2N-O-CH2-C(=O)-R <==> O2N-O-CH=C(-OH)-R
O2N-O-CH=C(-OH)-R + H2O <--==> HONO2 + HO-CH=C(-OH)-R
HO-CH=C(-OH)-R <--> O=CH-CHOH-R <--> HOCH2-C(=O)-R
O=CH-CHOH-R -ox by HNO3 or resulting NxOy-> HO2C-CHOH-R

There are two synthetic strategies: Depending on the stability of the nitrate ester towards water and acid or on the stability of the peroxyde link to the presence of Ag(+), Ag or Ag halide....
1°) Make 1,3-dichloroaceton, allow it to react with AgNO3 in water media to get 1,3-dihydroxyaceton dinitrate; then allow it to react with H2O2 in acidic media to get CDAP tetranitrate and CTAP hexanitrate variant.
2°) Make 1,3-dichloroaceton, allow it to react with H2O2 in acidic media to get CDAP tetrachloride and CTAP hexachloride variant.
Then allow it to react in saturated AgNO3 aceton or methanol solution to get the tetranitrate or hexanitrate variant.

Beware that the peroxyde are already a severe risk of handling (friction and shock)...this will be even worst with such unknown perfect OB nitrated peroxydes. I will try to calculate physico chemical parameters...

[Edited on 23-12-2014 by PHILOU Zrealone]

franklyn - 23-12-2014 at 21:53

Possible alternative nitrated peroxy ketone : Dimethylol acetone

http://patentimages.storage.googleapis.com/pdfs/US1955060.pd...

http://patentimages.storage.googleapis.com/pdfs/US4704479.pd...
— See variants on page 3

.

Ozone - 24-12-2014 at 07:16

DHA is reactive. It will condense with itself with least provocation. Almost anything you try and do with it will, as Philou indicates, make a pot full of brown tar.

In any case, that's how most of my experience with the compound has played out. Trace contaminants make this much worse.

In any case, whatever yield you get will not be spectacular.

O3

PHILOU Zrealone - 26-12-2014 at 10:48

As promised here are my calculations (*) of physico-chemical parameters for 3 previously exposed compounds, because they are unknown, I have taken both physical states as solid and liquid (I have the feeling they should all be taken as solids but just in case

)
You will see that all 3 compounds are highly potent explosives albeit all remarks I have done about it are to be taken seriously. Sensitivity to shock and friction must be very high, stability must be very low and storage highly unadvised. I you plan to make it remain on the safe side regarding quantities (<1g), avoid metals, avoid sunlight, avoid glassware and take all due precautions for handling and preparation (safety shield, safe distance, remote, face shield, gloves...)

1°)Dihydroxyacetone dinitrate ester (1,3-dihydroxypropanone dinitrate ester) - DHADN:
O2NO-CH2-CO-CH2-ONO2
Density if solid: 1,7438 g/ccm (if liquid: 1,604 g/ccm)
H^°_f: -201 kJ/mol (+/-5 kJ/mol)
VOD = 8564 m/s (8033 m/s if liquid)
Pcj = 264 kbar (223 kbar if liquid)

2°)Cyclo-Di-DiHydroxyAcetone-Peroxyde TetraNitrate ester (CDDHAPTN) - CycloDiAcetonPeroxyde TetraNitrate (CDAPTN):
(O2NO-CH2)2C(-O-O-)2C(CH2-ONO2)2
Density if solid: 1,942 g/ccm (if liquid: 1,7865 g/ccm)
H^°_f: -918,5 kJ/mol (+/- 45 kJ/mol)
VOD = 8845 m/s (8293 m/s if liquid)
Pcj = 209 kbar (177 kbar if liquid)

3°)Cyclo-Tri-DiHydroxyAcetone-Peroxyde HexaNitrate ester (CTDHAPHN) - CycloTriAcetonPeroxyde HexaNitrate (CTAPHN):
cyclo(-C(CH2ONO2)2-O-O-)3
Density if solid: 2,0257 g/ccm (if liquid: 1,860 g/ccm)
H^°_f: -328,6 kJ/mol (+/- 38 kJ/mol)
VOD = 9963 m/s (9307 m/s if liquid)
Pcj = 452 kbar (381 kbar if liquid)

Here are the datas from SMF-Engager detonator utility program:

CDAP-CTAP-CDAPTN-CTAPHN-DHADN.jpg - 673kB

(*)
a)
Density calculations where made via a method exposed in "Calculation of Densities of Organic Compounds from Contributions of Molecular Fragments" by A. A. Kotomin and A. S. Kozlov (ISSN 1070-4272, Russian Journal of Applied Chemistry, 2006, Vol.79, N°6, pp 957-966) (DOI: 10.1134/S1070427206060176)

b)
Heat of formations where calculated thanks to Hess thermodynamic laws, with use of average C-C bond dissociation energy and thanks to:

-An article provided by solo from PEP (Propellants Explos. Pyrotech. 2010, 35, 1–9) DOI: 10.1002/prep.201100100
"Taming the Beast: Measurement of the Enthalpies of Combustion and Formation of Triacetone Triperoxide (TATP) and Diacetone Diperoxide (DADP) by Oxygen Bomb Calorimetry"
by Alessandro E. Contini, Anthony J. Bellamy, and Leila N. Ahad
--> This allowed me to get acces to heat of formations of CDAP and CTAP.

-An article about CDAP and CTAP to get their cristal densities
"Decomposition of Triacetone Triperoxide Is an Entropic Explosion"
By Faina Dubnikova, Ronnie Kosloff, Joseph Almog, Yehuda Zeiri, Roland Boese, Harel Itzhaky, Aaron Alt, and Ehud Keinan
J. AM. CHEM. SOC. 2005, 127 , 1146-1159

-Rudolf Meyer's "Explosives" 4th edition
for datas about Ethylen glycol dinitrate (heat of formation standard liquid = 1603 kJ/kg)
--> -243,688 kJ/mol

-Heat of formation standard of:
aceton (l) = -41,0 kJ/mol
ethane (g) = 84,0 kJ/mol

-Here comes the idea...the heat of the following unrealistic reaction (but thanks to Hess it doesn't matter)
CH3-CO-CH3 + O2NO-CH2-CH2-ONO2 --> O2NO-CH2-CO-CH2-ONO2 + CH3-CH3
should be close to 0 kJ/mol (+/-5 kJ/mol) due to the fact it induces the breaking of 3 C-C bonds and the recombination of 3 C-C bonds...knowing the standard heat of formation of each compound but one allows to find the value for this unknown

.
Same procedure was used for CDAP and CTAP.

Quote: Originally posted by PHILOU Zrealone

Dihydroxyaceton is not nitratable directly because it is a strong reductor due to an equilibrium with 2,3-dihydroxy-propanal...
It has the ability to polymerize into dark polyphenolic stuffs (see its use as artificial suntanner).

Just as aceton (propanone) is unstable towards HNO3, so would DHA.
A mix of aceton and HNO3 usually ends up (in less than a minute) by boiling out nitrous fumes and runnaway, splashing all the beaker contain arround.

It could be nitrated by a derivated way via war gas lacrymator dichloroaceton and reaction with silver nitrate saturated solution...
Cl-CH2-CO-CH2-Cl + 2 AgNO3 --> O2N-O-CH2-CO-CH2-O-NO2 + 2 AgCl (s)

The halocetons are highly reactive towards substitution due to ceton group activation much more than allylic halide or benzylic halide...

The resulting dinitrate molecule will be very powerful explosive but might suffer hydrolysis behavior (and unstability-explosive runaway) because of the cetonic group and enol-ceton equilibrium what favors hydrolysis and set HNO3 free. This effect is seen in nitrosuggars (nitrate esters of suggars - nitrohydren) what are reputed unsafe to store.
Probably owing to some hydrolysis, the free HNO3 oxydizing the aldehyd group into carboxylic acid with self heating and runaway.
O2N-O-CH2-C(=O)-R <==> O2N-O-CH=C(-OH)-R
O2N-O-CH=C(-OH)-R + H2O <--==> HONO2 + HO-CH=C(-OH)-R
HO-CH=C(-OH)-R <--> O=CH-CHOH-R <--> HOCH2-C(=O)-R
O=CH-CHOH-R -ox by HNO3 or resulting NxOy-> HO2C-CHOH-R

There are two synthetic strategies: Depending on the stability of the nitrate ester towards water and acid or on the stability of the peroxyde link to the presence of Ag(+), Ag or Ag halide....
1°) Make 1,3-dichloroaceton, allow it to react with AgNO3 in water media to get 1,3-dihydroxyaceton dinitrate; then allow it to react with H2O2 in acidic media to get CDAP tetranitrate and CTAP hexanitrate variant.
2°) Make 1,3-dichloroaceton, allow it to react with H2O2 in acidic media to get CDAP tetrachloride and CTAP hexachloride variant.
Then allow it to react in saturated AgNO3 aceton or methanol solution to get the tetranitrate or hexanitrate variant.

Beware that the peroxyde are already a severe risk of handling (friction and shock)...this will be even worst with such unknown perfect OB nitrated peroxydes. I will try to calculate physico chemical parameters...

[Edited on 23-12-2014 by PHILOU Zrealone]

How about avoiding dihydroxyacetone entirely?

Arcuritech - 26-12-2014 at 22:18

The tautomerisation of DHA is going to cause problems if it is used as the starting reagent both in the case where nitration happens first and in the case where the cycloperoxide formation happens first. with that in mind, I suggest a similar plan to deltaH: avoid the DHA entirely.

A diether of acetone would be a good possibility as its peroxide would be insoluble and the ether could be hydrolyzed with an acid without disturbing the peroxide. Assuming the methyl diether as the start point one could even preform the hydrolyzation and nitration in the same step and evaporate the methyl nitrate (formed in a 6:1 ratio to the product) from the mixture to give the nitroperoxide.

[edited to correct a foolish naming problem]

[Edited on 2014-12-28 by Arcuritech]

Metacelsus - 27-12-2014 at 07:58

Do you mean diether? Diester implies a carboxylic acid.

Arcuritech - 27-12-2014 at 18:48

Quote: Originally posted by Cheddite Cheese

Do you mean diether? Diester implies a carboxylic acid.

Yes, I was a bit distracted by things happening out in the real world when I wrote that and I didn't proofread it. I'll edit it now.

franklyn - 28-12-2014 at 21:42

The evaluation by PHILOU Zrealone ( a heroic effort ) shows velocity of detonation is very much dependent on density. If the properties of the nitrated TACP are characteristic of other peroxides , the practical density will be less since the charge could not be safely pressed. If the melting point is lower than explosion temperature this may allow for the higher density solid upon cooling.
Organic peroxides (and ozone): Safety-oriented overview
http://digitalcommons.unl.edu/cgi/viewcontent.cgi?article=10...

Cyclo TriAcetone Peroxide HexaNitrate.gif - 5kB

Cyclo TriAcetone Peroxide HexaNitrate.gif - 5kB

The alternative reaction scheme proposed for nitration of peroxides has at least one example.
Nitrobenzoyl Peroxide
http://www.sciencemadness.org/talk/viewthread.php?tid=650#pi...

1,2,4,5-tetraoxanes discussed here _
Synthesis of five- and six-membered cyclic organic peroxides: Key transformations into peroxide ring-retaining products
http://www.beilstein-journals.org/bjoc/content/pdf/1860-5397...

.

[Edited on 29-12-2014 by franklyn]

PHILOU Zrealone - 29-12-2014 at 02:05

Just noticed that two "-" signes are missing:

Quoted from Philou:
-Rudolf Meyer's "Explosives" 4th edition
for datas about Ethylen glycol dinitrate (heat of formation standard liquid = -1603 kJ/kg)
--> -243,688 kJ/mol

-Heat of formation standard of:
aceton (l) = -41,0 kJ/mol
ethane (g) = -84,0 kJ/mol

Arcuritech - 29-12-2014 at 02:51

Two ideas regarding the sensitivity and packing problem.

The nitroperoxide (cyclonitroperoxide? TCNP? We need a shorter name for this stuff.) is likely soluble in nonpolar organics. Getting almost ideal density may be as simple as dissolving and then redepositing it in layers.
The sensitivity of this compound seems more than a little hard to guess at, and assumptions of instability are almost as tenuous as those to the contrary. For all we know those six nitrate groups have enough mass and volume to keep thermal/vibrational/kinetic strain away from the peroxide groups (though it doesn't seem very likely).