Sciencemadness Discussion Board - Organic peroxides

Organic peroxides

plasma - 21-5-2002 at 09:11

What is this and how can I make it.

madscientist - 21-5-2002 at 11:34

Organic peroxides are a type of chemical. Many are explosive in nature. They are organic compounds (compounds based off of a carbon structure) that contain a peroxide group (a pair of oxygen atoms joined by a single bond). There are many explosive organic peroxides: tricylcoperoxyisopropanone (CH3COOCH3)3 (commonly known as trimeric acetone peroxide) methyl ethyl ketone peroxide, HMTD... I am thinking that it would be possible to form aceteldehyde peroxide and / or formaldehyde peroxide.

plasma - 21-5-2002 at 11:35

Is it possible to get a receipt on a organic peroxide ?
Bt the way, I found Methylketonperoxide in my garage, this sounds like a organic peroxide to me but I isn't exploding. It just burns vigoursly. Does it have to be in a confined space to explode ?

Polverone - 21-5-2002 at 11:36

Methyl ethyl ketone peroxide is indeed an organic peroxide. It is a poisonous, irritating, explosive liquid. It is used to catalyze the hardening of resins, as with fiberglass. I assume this is how you come to have some in your garage. However, the stuff sold as a catalyst it certainly NOT pure MEK peroxide! Here's some information from Smith Fiberglass about their MEK peroxide catalyst:
Methyl ethyl ketone peroxide: 0-10%
Dimethyl phthalate: 10-60%
Hexylene glycol: 1-10%
Methyl ethyl ketone: 0-5%
Hydrogen peroxide: 0-5%

Not too long before the Forum went down, there was a thread on MEK peroxide. It can be prepared like acetone peroxide, substituting methyl ethyl ketone for the acetone. It can be set off by shock and heat. Unlike many other organic peroxides, it is a liquid, so it can't form dangerous crystals. However, the limited information available should discourage an inexperienced experimenter from preparing it.

plasma - 21-5-2002 at 11:38

The bottle I found was a catalyst. The label says that it contains 30-60% methyl ethyl keton peroxide. But it won't explode. It just burns vigoursly. I need a explosion powerfull enough to set of AN, but it doesn't seem like organic peroxides will work. Do you now about any ways to make the AN more sensitive (much more).

madscientist - 21-5-2002 at 11:40

I would forget trying to set off pure ammonium nitrate. I would make ANFO with it (about 96% prilled ammonium nitrate, 4% diesel or other liquid hydrocarbon fuel). You will still need a relatively powerful detonator. If you do not have the resources to prepare common detonators (for example, lead azide, mercury fulminate, etc.) you will need to make organic peroxides. Look here for more information on organic peroxide explosives like HMTD and AP. http://wind.prohosting.com/megaback/megalomania/index.html

plasma - 21-5-2002 at 11:40

I found this information on :

ACETONE PEROXIDE - mix by volume 3 parts 6% peroxide to 2 parts acetone in a
glass jar, leave 30 min, add 2 parts hydrochloric acid and let sit overnight.
White crystals will form out of the mixture, these are the explosive which are filtered and dried.
HMTD - Dissolve 2 parts hexamine in 4 parts 6% peroxide, add 2 parts hydrochloric acid and let sit overnight. A white fluffy powder will form which is HMTD, filter and dry as with acetone peroxide.
These are explosives that are usually underestimated in power and sensitivity.
4 grams of either of these will take off a hand of anyone careless enough to
make and misuse this material.

Many files recommend using them strait for detonation of ammonium nitrate, don't bother, it won't work.
This last sentence is very confusing. :/

Thanks for the wonderful link madscientist

Polverone - 21-5-2002 at 11:41

That's a pretty good writeup that you found. Note that the fireball picture on the page is certainly from a *deflagration* - quick burning - of acetone peroxide rather than a detonation. When exploding, I have seen at most a dull orange flash with acetone peroxide. The last sentence on the page may mean a couple of things: 1. Ammonium nitrate will not explode with initiation from organic peroxides. This is perfectly reasonable since pure ammonium nitrate is *extremely* difficult to detonate, and there is in fact debate whether the pure compound will every experience a self-sustaining explosion. 2. Ammonium nitrate blasting agents will not explode with initiation from organic peroxides. I would beg to differ with this. Success in setting off ammonium nitrate blasting agents will vary with the composition of the agent, its manner of preparation, and choice, quantity, and placement of the initiating agent.

plasma - 21-5-2002 at 11:42

I have successfully made AP but one thing is bothering me, the process needs very much acid when using 6% hydrogenperoxide, here are my ideas:
(CH3)2CHOH O2 -} (CH3)2CO H2O2
isopropyl dioxide -} Acetone Hydrogenperoxide

My problem is how to oxidize the isopropyl, can it can it be done by bubbling carbondioxide through it like this:

(CH3)2CHOH 2CO2 -} (CH3)2CO H2O2 2CO

Or like this:

(CH3)2CHOH CO2 -} (CH3)2CO H2O2 C

Are any of this reactions correct ?

I belive that these reactions would give relatively pure Acetone and Hydrogenperoxide, if they are correct.
Please correct me if I'm wrong

Polverone - 21-5-2002 at 11:42

Your equations are confusing. Please consider using the + symbol. Carbon dioxide will not easily oxidize anything but the most powerful reducing agents. If you hope to change isopropanol by bubbling CO2 through it you're out of luck. Please clarify if I've misinterpreted what you're saying.

plasma - 21-5-2002 at 11:43

I looks like the spell checker removes the + symbol after checking. It seems like you got the point, if not I will try to make it a bit clearer. I read in a encyclopedia that if isopropanol is oxidized it will create acetone and hydrogenperoxide. My calculations said that this solution would contain 64% acetone and 36 % hydrogenperoxide (by weight). With hydrogenperoxide as concentrated as this, the amount of acid used in AP processing could be lowered very much. So my idea was to oxidize the isopropanol by bubbling CO2 trough it (which apparently won't work).
Do anyone know isopropanol can be oxidized

madscientist - 21-5-2002 at 11:43

I don't see why the oxidation of isopropanol would form hydrogen peroxide. Isopropanol would probably be oxidized by KMnO4. I find the following to be more likely:
6(CH3)2HCOH + 2KMnO4 --> 5(CH3)2CO + (CH3)2HCOH + 4H2O + 2KOH + 2MnO

plasma - 21-5-2002 at 11:43

I found this equation in a encyclopedia at my school:
(CH3)2CHOH + O2 -} (CH3)2CO + H2O2

Polverone - 21-5-2002 at 11:44

You will notice that your encyclopedia equation is using oxygen, not carbon dioxide. Also, I do not believe that isopropanol deteriorates in ambient conditions on exposure to atmospheric oxygen. In other words, if the reaction does take place as shown (which seems kind of dubious - H2O2 is not a very stable molecule), it almost certainly takes place under extreme reaction conditions - high temperatures/pressures, or maybe with the aid of a catalyst. What encyclopedia was this from, BTW?

plasma - 21-5-2002 at 11:45

I know the encyclopedia used oxygen not carbon dioxide, that was just my theory on oxidizing the isopropanol since I can't get pure oxygen.
I found the equation under "isopropanol" in a Norwegian encyclopedia which is called "Aschehoug".
The encyclopedia said nothing about pressure, temperature or catalysists.
BTW, I made AP today, and now just one hour after I added acid, a 5mm layer of crystals has appeared (tube dia. 5 cm). This is the ingredients that I used :

36 ml Acetone
24 ml 1-5% Hydrogenperoxide
3 ml 50-60% Sulfuric acid

Considering that it just have been standing for one hour, is this a high yield ?

(Yes I'm Norwegian)

madscientist - 21-5-2002 at 11:46

Excerpt from one of my chemistry texts:

There are many organic peroxides and hydroperoxides.
Peroxo carboxylic acids, for example peracetic acid,
CH3C(O)OOH, can be obtained by the action of H2O2 on
acid anhydrides. The peroxo acids are useful oxidants
and sources of free radicals, for example by treatment
with Fe(2+) (aq). Benzoyl peroxide and cumyl
hydroperoxide are moderately stable and widely used
where free radical initiation is required, as in
polymerization reactions.
Organic peroxo compounds are also obtained by
autoxidation of ethers, alkenes, and the like, on
exposure to air. Autoxidation is a free radical chain
reaction initiated by radicals generated by
interaction of oxygen and traces of metals such as Cu,
Co, or Fe. The attack on specific reactive C-H bonds
by a radical (X*), first gives R* and then
hydroperoxides that can react further.

RH + X* --} R* + HX
R* + O2 --} RO2*
RO2* + RH --} ROOH + R*

Explosions can occur on distillation of oxidized
solvents. These solvents should be washed with
acidified FeSO4 solution or, for ethers and
hydrocarbons, passed through a column of activated
alumina. Peroxides are absent when the Fe(2+) + SCN-
reagent does not give a red color indicative of the
Fe(SCN)(2+) ion.

plasma - 21-5-2002 at 11:46

I have still not made HMTD succesfully, and I think it's because my fuel sticks isn't methamine. My fuel sticks are black, burn very slow and smells and looks a bit like charcoal. They aren't soluble at all. The name of the fuel sticks are "Solid fuel sticks" and the brand is "Jimmy" (From America)
Where to get methamine fuel tablets ?
Thanks

madscientist - 21-5-2002 at 11:47

Hexamethylenetetramine (also called "hexamine" or "methanamine") is also sold as "Urotropine", a urinary antiseptic.

plasma - 21-5-2002 at 11:47

This is ment for reodor felgen, if he has found his way into the new forum.
(Norwegian)
Ammonium nitrat fåes kjøpt i sports butikker som isposer for ca. 16 kr. Det er veldig enkelt og lage natrium nitrat av ammonium nitrat. Det gjøres slik :

NaOH + NH4NO3 -> NaNO3 + NH4OH

Bland et mol natrium hydroksyd med et mol ammonium nitrat i vann. Dette bør gjøres på et godt ventilert sted siden det frigjøres mye ammonium hydroksyd gass. Nå gjenstår det bare å koke løsningen for å få fordampet vekk ammonium hudroksydet og vannet. Krysstaller kommer til syne etter vært.
Natrium nitrat har de samme egenskapen som kalium nitrat men virker mer oksyderende. (har ikke mye å si)

Jeg tar gjerne imot mer informasjon om heksametylentetramin tablettene dine.(ice8@sol.no)
Vet du for man kan få tak i salpetersyre ?
Jeg bor i en liten bygd i vest-telemark.

reoder felgen - 21-5-2002 at 16:28

Thanks plasma.
dette er også slik jeg får tak i NaNO3 og NH4NO3, men glemte å ta det med når jeg lagde listen. er du sikker på at gassen som dannes er NH4OH og ikke NH3 + H2O? men det betyr forsåvidt ikke så mye. Heksametylentetramin kjøpte jeg på en liten "chemist sypply house" (kommer ikke på noe bra norsk ord), men de leverer først og fremst til skoler o.l. tviler på at du har den samme butikken i telemark. virket som en "famile greie" altså ikke en kjede.
salpetersyre har jeg aldri sett og tviler sterkt på at jeg noen gang kommer til å få se det. vurderer å lage det ved å blande så ren som mulig svovelsyre med kalsiumnitrat (ikke kalium) for så å filtrere kalsiumsulfatet bort på en eller annen måte. virker bra for da trenger jeg ingen destilering!

plasma - 21-5-2002 at 16:29

(Norwegian)
Kunne du kjøpt heksametylentetramine til meg og sendt det med postoppkrav. Jeg tror ikke jeg kommer meg til Kristiansand med det første. Hvis du mailer meg på denne adressen ice8@sol.no kan jeg sende deg navn og adresse. Jeg er svært takknemlig hvis dette er gjennomførbart. Det hadde også vært interresant å vite hva slags andre ting de selger i denne butikken også.
Thanks

PHILOU Zrealone - 21-5-2002 at 16:29

I'm not norvegian although, I understand German, Dutch and English quite wel, I can figure out some terms in Norvegian!
Anyway:
Urotropine/Hexamine/hexamethylenetetramine can be done quite easily from conc NH3 and conc CH2=O solutions:
Add an excess of freezing cold NH4OH solution (max is 30% NH3 per weight) to a freezing cold one of CH2=O (formol/formaldehyde solution is max 40% by weight over it deposit a precipitate of polyformal).Mix the two in stoechiometric amounts following the formula:
6CH2=O + 4NH3 --> C6H12N4 + 6H2O
Taking care to have a slight excess of NH3 solution of 20 to 30%!
It will heat a little reason why we have cooled the solution prior to reaction-sothat reactants are not lost in gases form and inhalated by experimentator.
Allow to stir for an hour and then warm up to 40°C and allow to evaporate as long as it needs to get cristaline/solid!Exces NH3 will take off quite fast! Yield 100%!

PH Z

plasma - 21-5-2002 at 16:30

How can CH2=O be made ?
Thanks

madscientist - 21-5-2002 at 16:30

Here's a good opportunity for this:
I'm theorizing that CH2O could be prepared from CH2Cl2 and NaOH.

CH2Cl2 + 2NaOH --> CH2(OH)2 + 2NaCl --> CH2O + 2NaCl + H2O

PHILOU Zrealone - 21-5-2002 at 16:30

CH2=O can indeed be done by CH2Cl2 in the presence of NaOH (solid); the process require a long time if both reactants aren't brought into contact by an amphiphil solvant...would you expect Water soluble NaOH to be soluble in unwater soluble CH2Cl2?
But once it is done, a vigorous exothermic reaction may take place and possibly generate in situ suffocating gases like Cl-CH2-OH (a very toxic and reactive gas), CH2=O, Cl-CH2-O-CH2-OH (must also be quite unfriendly)!
If it doesn't start on its own, you would have to heat a little but (dichloromethane is quite volatile) and no big heat can be acheived unless under pressure...what I strictly discourage you to do since the container might explode du to exothermic reaction and volatilisation of volatile liquid and libération of gases!!!
A much wiser way to make CH2=O is by reacting CH3OH with a strong oxydiser in acidic media!
I would recomand to make a concentrated solution of KMnO4 or K2Cr2O7 in H2SO4; then to drop drop by drop methanol in it(under agitation)...then try to keep T arround 40°C (by cooling if it goes too exothermic) or by gentle heating!
Formaldehyde will form and volatise (thanks to the fact it is a gaseous aldehyde and thanks to the 40°C); part of it will dissolve in the solution (since it is quite avid of water) and perform a further oxydation into formic acid and carbonic acid!
The use of a cold trap with stirred water in it will allow you to catch most of its gaseous evolution!
Water boild at 100°C
Methanol at 65°C
Formic acid at 101°C
Carbonic acid at ambiant pressure (CO2 + H2O)
So it is very important to keep the reactor at 40°C to avoid boiling the methanol!
CH3-OH + -Oxydiser/H(+)-> CH2=O + H2O
CH2=O + -O-> HCO2H -O-> H2CO3 --> CO2 + H2O
CH2=O + H2O --> CH2(OH)2 (hydrate of methanal)

You could also use a clod trap with NH4OH sothat the CH2=O will be catched immediately as CH2=NH that will condensate into hexamine!
CH2=O + H2NH --> CH2=NH + H2O
6CH2=NH --> C6H12N4 + 2NH3(g)

Enjoy!
BTW, Madscientist and others, I have replied to many treads in all chapters of this NG!

PH Z

PHILOU Zrealone - 21-5-2002 at 16:31

Another idea to make CH2=O:
Make Ca formate, dry it:
Then heat it under a vigorous flame (the rector must be closed vs the flame and a cold trap has to be set on since aldehydes and cetons are very flamable and risks of fire can result!!!):
Ca(O2CH)2 --> CaCO3 + CH2=O
BTW:the same procedure is was used to make aceton...CaCO3 can be reconverted into Ca carboxysalt by agitation with the acid (vinegar)
Ca(O2C-CH3) --> CaCO3 + CH3-CO-CH3
And if I remember wel:
Ca(O2C-CH3)2 + Ca(O2C-CH2-CH3)2 -->
CaCO3 + CH3-CO-CH3 + CH3-CO-CH2-CH3 + CH3-CH2-CO-CH2-CH3
So it is a convenient way to make aceton, MEK and diethyl ceton (3 pentanone).

A final aspect I think to remember is:
Ca(O2CH)2 + Ca(O2C-CH3)2 --> CH3-CO-CH3 + CH3-CH=O + CH2=O + CaCO3

Tath's all folks!
PH Z

plasma - 21-5-2002 at 16:31

Thank's for the informative posts.
Let me see if I have understanded this correct. I mix 68% freezing cold 35% CH2O with 32% freezing cold conc NH4OH solution.
Then stir it for an hour and evaporate the liqiud at 40 C. Hexamine will crystalize.

BTW, I mentioned this procedure to a friend of mine and told him all I needed was formaldehyde. Supriseingly he had a 1 litre bottle of it in his garage. (He is interested in biology and has used it for preserving plants).
I bought half a litre of him.

PHILOU Zrealone - 21-5-2002 at 16:32

You have almost understood everything but let's compare:
what you said:
"I mix 68% freezing cold 35% CH2O with 32% freezing cold conc NH4OH solution. Then stir it for an hour and evaporate the liquid at 40 C. Hexamine will crystalize."
with what I said:
Add an excess of freezing cold NH4OH solution (max is 30% NH3 per weight) to a freezing cold one of CH2=O (formol/formaldehyde solution is max 40% by weight over it deposit a precipitate of polyformal).Mix the two in stoechiometric amounts following the formula:
6CH2=O + 4NH3 --> C6H12N4 + 6H2O
Taking care to have a slight excess of NH3 solution of 20 to 30%!

Why the hell 68% CH2=O (35% solution) with 32% NH3 (32% solution)?
What is the stoechiometry I proposed you, where is the excess NH3?
You add an excess CH2O vs NH3; your cristallisation will thus contain some polyformal what is a big problem when brought in contact with HNO3 --> very strongly exothermic runaway will occure!

Let see my explication deeper:
30% NH3 solution, means 300g of NH3/kg or 17,64 mole/kg solution!
40% CH2=O solution, means 400g of CH2=O/kg or 13,33 mole/kg solution!
Following the equation I have written:
6 moles of CH2O react with 4 moles of NH3!
Thus knowing that:
we have 17,64 mole/kg of NH3(30%), and 13,33 mole/kg of CH2O(40%); we need: 226,76g NH3 solution for 450,12g CH2O solution!

With the slight 25% excess of NH3 solution (to ensure 100% yield and no CH2O that is bad for further HNO3 exposure):
283,45g NH3 solution for 450,12g CH2O solution:
This makes 38,64% NH3 sol for 61,36% CH2O sol!

In you case you have 35% instead of 40% formol and 32 instead of 30% NH3; you will thus need:
450,12g*40/35= 514,43g CH2O solution and 283,45g*30/32= 265,73g NH3 sol.
Thus you would need:
34,1% NH3 solution(32%) for 65,9% CH2O solution or 341g/659g; you should get 179,5g Hexamine!

You were not far off but stil you might have had trouble with excess formol, better be cautious and not forget the 25% excess ammonia!

PH Z

plasma - 21-5-2002 at 16:33

Made hexamine sucessfully today. I didn't have any conc NH3 solution left so I used 10% clear houshold ammonia instead. (adjusted the amounts) The yeld was not as high as expected but satisfying.

PHILOU Zrealone - 16-8-2002 at 07:48

The only reason why conc reactants are used is that they are already quite diluted if concentrated (30-40%) --> 70-60% water that has to be evaporated!

PH Z

paraldehyde triperoxide

vulture - 20-8-2002 at 08:48

Since this topic is about organic peroxides, let's talk about paraldehyde peroxide. Paraldehyde are 3 polymerized acetaldehyde (ethanal) molecules connected by the oxygen molecule of the aldehyde.
It is made by heating acetaldehyde with conc H2SO4.

Paraldehyde triperoxide would have the structure shown in the image. It might be very similar to AP, but the synthesis can't be, according to me atleast. With AP the molecule ring is formed during peroxidation, here the peroxidation would take place after the ring closure,which seems quite difficult. Or one could ofcourse try ring closure with H2O2 present.

paraldehyde peroxide.JPG - 5kB

madscientist - 20-8-2002 at 17:38

I have attempted to prepare acetaldehyde peroxide using H2O2, acetaldehyde, and H2SO4. It failed, probably because the acetaldehyde was (this is my hypothesis) just being oxidized to acetic acid. I didn't expect it to succeed, but what the hell, why not try...

I guess that failed experiment rules out the possibility of preparing formaldehyde peroxides.

CH3CH(OH)(OOH) ----> CH3COOH + H2O

So the first step, reaction of CH3CHO with H2O2, results in the oxidation. I'm not sure if H2SO4 would be required for that reaction - I think that CH3CHO would hydrate easily to CH3CH(OH)2, and so it would easily carry out a parallel reaction with H2O2 to form CH3CH(OH)(OOH)

Thanks

Ramiel - 24-8-2002 at 02:41

This is similar to the process I had seen, and overcomes the problem of excess oxidation of the CH2O, thanks a lot for posting.

problems with AP synth

Nevermore - 26-5-2003 at 10:12

I'm having some strange troubles with AP synt using 3% h202 and pure acetone, i follow the recipe on megalomania's but i get no yeld at all. The only changes i made are using 15ml acetone and 100ml h202, and then 7ml 40% h2so4. i cared the temp was always around 0, added slowly, stir in ice and let it rest in fridge for 2 days but not even a cristal..also tried with HCL but no change..i start to suspect this h202 is no good since is written "stabilised h2o2" maybe it has some compound that prevents the reaction to occurr? please advice any hint you think could be useful! thanks!

sorry

Polverone - 26-5-2003 at 16:31

Acetone peroxide has been covered to death elsewhere. I've heard people claim success with 3% peroxide, but I think you would be much better off with a higher concentration solution. Methods of H2O2 concentration are scattered about this forum and others.

Krypton - 26-5-2003 at 17:48

Here some knowledge to a old new synthesis
by me to a meltable and thermic insensitive
dicyclic peroxide.

dicycloperoxide

It`s a fine powder, chemical stable and
insensitive against shock and high temperatures
with a sweet odour.

mp ~100 C
dc >350 C, (ignition)
ev ~ 7500 m/s

Blind Angel - 26-5-2003 at 18:52

Benzoyl Ketone + AP normal reaction?
Look like Benzoyl Peroxyde but with an added peroxo bridge

[Edited on 27-5-2003 by Blind Angel]

Formaldehyde

blip - 26-5-2003 at 20:06

I've seen CH2O produced by a rather powerful spark underwater using graphite electrodes.

madscientist - 26-5-2003 at 20:23

That's the bicyclic form of cyclohexanone peroxide.

PHILOU Zrealone - 4-6-2003 at 04:40

I really think we should investigate cyclohexanedione peroxyde!

O=C(CH2-CH2)2C=O + 2H2O2 --> (HOO)(HO)C(CH2-CH2)2C(OH)(OOH)

This should lead to a relatively unsensitive polymer that has better OB than Aceton peroxyde.
(-O-O-)2C(CH2-CH2)2C(-O-O-)2C(CH2-CH2)C=
As I have proven many times, the higher the molecular weight the lower the sensitivity, the higher the melting point, the higher the density and the better the VOD!

PHILOU Zrealone - 4-6-2003 at 04:41

And of course... nitro and dinitrocyclohexanone peroxydes

Iv4 - 6-6-2003 at 02:43

3% h202 should work just fine(ignoring the worthless yield,ofcourse).Chances are (with all the wank about terrorism and all)there was something in you'r h202 to kill the reaction making AP.Perhaps if you'd warm to to a somewhat higher concentration and then repeat the experiment we'd find out what's hapening.

Sorry for not havng anything to contribute as far as cyclohexanonan peroxide goes but a just a few questions:
<ol>

Was the spark in pure water,tap water or was there anything mixed with it?

Do you have any idea about the charge itself?
</ol>

Nevermore - 24-7-2003 at 10:24

those experiments have been performed by pure water, tap water, with carbon rods, and by tungsten rods in saccarose solution. carbon is needed in the reaction.

more ...

KABOOOM(pyrojustforfun) - 4-9-2003 at 18:39

heat citric acid to 100°C to make sure it's dehydrated. add conc sulfuric acid to get acetone dicarboxylic acid. I think this is the reaction:
H2SO4 + HOOCCH2C(COOH)(OH)CH2COOH => HOOCCH2COCH2COOH + 2H2O + SO2 + CO2
add the mix drop by drop to ice cold (preferably conc) H2O2 hoping to get di/tri/..mer of peracetone dicarboxylic acid peroxide. a cyclic dimer:
<img src="http://www.angelfire.com/rnb/pjff/padcp.gif">
C10H12O16 => 10CO + 6H2O
Penguin Dictionary of Chemistry says phloroglucinol chemically behaves like both 1,3,5-trihydroxybenzene and triketone of cyclohexane( >(-CH2-C=O-)3> ). now think about its peroxidation! (woW <img src=images/smilies/shocked.gif>

Edit: fixed the img

[Edited on 1-12-2003 by KABOOOM(pyrojustforfun)]

shadeT - 7-9-2003 at 04:40

does someone have some information about benzoyl peroxide ? i found some info on xinventions forum ... but nothing else ...

benzoyl peroxide

Mephisto - 7-9-2003 at 08:50

CAS number: [94-36-0]
melting point: 103 -106 °C (may explode when heated)
sparingly soluble in water or alcohol
soluble in benzene, chloroform, ether
made from: benzyol chloride and sodium peroxide
use: Source of free radicals for industrial processes. Oxidizing agent in bleaching oils, flour, etc.; catalyst in the plastics industry; initiator in polymerization.

From the Merck Index

[Edited on 7-9-2003 by Mephisto]

a123x - 21-9-2003 at 14:12

Any ideas on the stability or power of methyl isobutyl ketone peroxide? I was thinking of ordering some methyl isobutyl ketone for the purpose of making the peroxide of it but want to hear some thoughts about it before I bother ordering it.

KABOOOM(pyrojustforfun) - 30-11-2003 at 21:07

Krypton:
<blockquote>quote:<hr>Here some knowledge to a old new synthesis by me to a meltable and thermic insensitive dicyclic peroxide. <a href="http://www.sciencemadness.org/scipics/dicycloperoxide.JPG" target=_blank>dicycloperoxide</a> It`s a fine powder, chemical stable and insensitive against shock and high temperatures with a sweet odour. mp ~100 C dc >350 C, (ignition) ev ~ 7500 m/s<hr></blockquote>cyclohexanone peroxide isn't C6H10<(OO)2>C6H10 it is<img src="http://www.angelfire.com/rnb/pjff/chnp.gif">
from the condensed chemical dictionary:
cyclohexanone peroxide  (1-hydroperoxycyclohexyl
  1-hydroxycyclohexyl peroxide)
  C6H10(OOH)OOC6H10OH.
 Properties: Grayish paste; insoluble in water; soluble
  in most organic solvents.
 Hazard: Dangerous fire risk in contact with organic
  materials. Strong oxidizing agent.
 Shipping regulations: (Rail) (not over 50%) Organic
  Peroxide label; (50-85% Organic Peroxide label.
  Not acceptable passenger. (Air) (not over 50%)
  Organic Peroxide label;(50-85%) Organic Peroxide
  lable. Not acceptable passenger. (Over 85%) Not
  acceptable.

7500 is too much. assuming it's quite less explosive than AP, I doubt its VOD to be higher than 5000 m/s

methyl isobutyl ketone

kleineskind - 13-12-2003 at 22:09

I found a local hobby shop that sells a lot of really cool chemicals. not in their chemistry section, but their painting section I found a container of methyl isobutyl ketone. I plan on experimenting with it to see what kind of things can be formulated from it. making a peroxide may be complicated due to the fact that there is little information if not none at all on how to procure such a substance. I enjoyed the method to create hexamine. I plan on implementing the nitration of hexamine eventually. hexamine has been the most interesting substance to me. but I plan on mixing methyl isobutyl ketone with many explosives so I can determine its application for mixtures. toluene was also available to me in its pure form at this hobbyshop. let me just say that the best place to get chemicals is from frey scientific, but because they dont sell to people that do not belong to a company or a school, the best places are 1- places that deal with photography, gardening, hobby shops, hardware stores, drug stores, paint shops, and crafting. ebay has been my recent love. you can buy 8 pounds of potassium nitrate for a awesome price- $10.00!

sylla - 14-12-2003 at 13:38

BTW, I've heard that dihydroperoxypropane could be formed using the common acetone/H2O2. I haven't done any search on it (I apologize if it is the first link on google :p). Have someone tried it ?

It's oxygen balance (-70%) is far better from other peroxides such as the acetone one (di/tri or tetra meric) and DPPP and a bit betterthan HMTD and TMDD. It's density is around 1.3 (following ACD/ChemSketch software).

But I'm sure with all these properties someone here had already tried it !

KABOOOM(pyrojustforfun) - 17-12-2003 at 18:59

it formes as an "intermediate" in AP synth. I doubt there's any way to prevent it from further reactions (which form AP) then isolating it

Theoretic - 19-10-2004 at 08:13

I wonder, is acetone peroxide soluble in anything?

Axt - 19-10-2004 at 09:17

Conveniently, its fairly soluble in Acetone (I think more-so in DCM), why you ask?

Rosco Bodine - 19-10-2004 at 10:59

AP is fairly soluble in anhydrous isopropanol .

But a more interesting AP solution is coprecipitated AP / MEKP ~ 50/50 , which
separates directly from synthesis as a reasonably pure anhydrous liquid ,
making it easier to isolate than either
AP or MEKP made separately .

Theoretic - 20-10-2004 at 00:08

Just asking, might be useful for storage/separation from the reaction mixture.

[Edited on 20-10-2004 by Theoretic]

Chris The Great - 31-7-2005 at 02:39

Quote:

Originally posted by sylla
BTW, I've heard that dihydroperoxypropane could be formed using the common acetone/H2O2. I haven't done any search on it (I apologize if it is the first link on google :p). Have someone tried it ?

It's oxygen balance (-70%) is far better from other peroxides such as the acetone one (di/tri or tetra meric) and DPPP and a bit betterthan HMTD and TMDD. It's density is around 1.3 (following ACD/ChemSketch software).

But I'm sure with all these properties someone here had already tried it !

I recently became interested in this peroxide and other non-tradition peroxides. Alot of organic peroxides have not been experimented much with, mainly HMTD, AP, etc. It forms, as already stated, as an intermediate in AP synthesis. Another peroxide also forms, basically two of these joined together by a peroxide bond:
HOOC(CH3)2OOC(CH3)2OOH
Both of these are soluble in water, but I think they could easily be extracted using something like methylene chloride or other non-polar non-water-miscible solvent. I would use methylene chloride because of it's low boiling point.

According to a journal on AP I read, it mentions that the peroxide you mentioned, HOOC(CH3)2OOH was isolated in 12% yield when 50% H2O2 and acetone where reacted in a 1:1 molar ration in the absence of the hydrogen ion (no acid). Hence, when you mix H2O2 and acetone you get a bunch of non-cyclic peroxides, the H+ caused them to form cyclic derivatives- the well known acetone peroxide.

When I attempt this procedure, I will mix H2O2 and acetone in a 2:1 molar ratio, with no acid. After several days I will extract with methylene chloride, and then gently boil if off along with the remaining acetone (the remaining acetone will also be picked up by the methylene chloride) to get the non-cyclic peroxides.

The Encyclopedia of Explosives gives some information on organic peroxide properties, which is based on structure. It appears that these peroxides should be quite stable (relative to other organic peroxides that is). For the C(OOH)2 type peroxide, explosive properties are listed as:
Polymeric peroxides formed as a decomposition product are extremely explosive

For HOOCOOCOOH type peroxides, it lists:
Very slight explosive properties

These could obviously be detonated but as organic peroxides go they seem to be quite stable. It will be interesting to attempt to isolate them.

Another interesting thing I noticed in that AP journal was that it mentioned "in the presence of the hydrogen ion, all three abducts have been isolated with the cyclic trimer being the predominant product in concentrated solutions."
Hence, it would appear that in lower concentrations of H2O2 and acetone, such as with 3% H2O2, the equilibrium shifts over to the non-cyclic peroxides, and hence a much larger amount of acid is required to push it back towards the cyclic trimer.

I recently picked up a liking for such 'non-traditional' peroxides and hope to prepare a couple of them in the near future. Some other ones I am interested in are the alkyl hydroperoxides, for example methyl hydroperoxide, CH3OOH. It's a liquid, seems to be sensitive from what I've read but info is very limited. The Encyclopedia says that it explodes violently (I would think so!) upon jarring or heating.
The explosion should follow:
CH3OOH --> CO + H2O + H2
It is prepared like this:
(CH3)2SO4 + 2H2O2 + 2KOH --> 2CH3OOH + K2SO4 + 2H2O
For the ethyl and isopropyl derivatives it says it is seperated by vacuum distillation but I'm not in a hurry to do that! Doesn't say anything about isolating the methyl hydroperoxide

I'm hoping it can be seperated by using methylene chloride as well, as thats simple. Unfortunately, "sensitive to jarring especially at warm temps" makes me wonder about the wisdom of boiling of a solvent. I think I'll let it sit in a cool dark location to evaporate.

Axt - 31-7-2005 at 05:05

View: http://pulse.webtop100.net/images/methylhydroperoxide.zip 17pg 3.something MB

In German though. I had chemoleo translate some of it quite a while back, guess he wont mind me posting it. This regards the calcium/barium salts of methylhydroperoxide.

Quote:

Anyway, it says, 'crystalline barium hydroxide (presumably referring to Ba(OH)2*8H2O), or even calcium hydroxide, is easily dissolved in a concentrated aqueous solution of methylhydroperoxide.
Salts are formed, which are very soluble in H2O, and which can be isolated by evaporation at as low a temperature as possible (great care to be taken!)'.

But in the end, its quite hard to get any decent yield of the alkylhydroperoxides. I think there was a patent related to mixing methanol/H2O2 and salting out the hydroperoxide followed by distillation, give the patent office a search for methylhydroperoxide etc. but I think it was still <10% concentration.

Might be worth trying to extract dimethylolperoxide (formaldehyde/H2O2) with a more volatile solvent, as it wants to detonate if evaporated from water .. know that first hand. I think theres a Pb salt of this in PATR2700. Theres a soluble hydroperoxide of hexamine as well, also an insoluble one by using HNO3 check vol.8, H82.

Chris The Great - 31-7-2005 at 09:49

Quote:

I can't read German but at least that gave me a good idea of the synthesis as well as the yields. I guess 100g dimethylsulfate --> 7g methyl hydroperoxide is pretty poor. Couldn't find the patent but I would prefer to prepare it in the pure form, to make other interesting compounds and also for a small explosion test. I certainly don't want to make these to make big booms, I just wanna make them because they are interesting and unusual.

Thanks for the info! Can someone kindly translate the synthesis, which starts on page 12? It's fairly short. I can get the general idea but it would be nice to know exactly what they did, and not just generally what they did. Doesn't look that hard but it would be problematic if a sentence that I thought meant stir vigoursly actually means stirring causes detonation, etc.

organic peroxides

((Blasta)) - 16-8-2005 at 09:05

Chris, sounds like you have some great ideas. Have you tried producing Methyl Ethyl Ketone Peroxide yet? I think you'll find that the VoD of this stuff is pretty good...and when mixed with Ammonium Nitrate can be quite powerful. Never mind TCAP...

Chris The Great - 16-8-2005 at 20:09

No, unfortunately I have not....

I haven't found MEK here (at least not in a product that it could be easily extracted from), but I haven't actually looked that hard.

If I see some I will definately pick some up though.

((Blasta)) - 16-8-2005 at 22:07

Quote:

Originally posted by Chris The Great
No, unfortunately I have not....

I haven't found MEK here (at least not in a product that it could be easily extracted from), but I haven't actually looked that hard.

If I see some I will definately pick some up though.

It is avaliable, but getting scarcer due to its effects on health. Try Industrial Plastics and Paint, Cloverdale Paints, ICI paints, General Paints** I know they have a tonne of the stuff at dirt cheap prices. MEKP with an addition of a NITRATE is very fun to detonate. Its quite powerful

oh, mixed with finely powdered Ammonium Nitrate 9:1 ratio proves to be awesome. No idea on the VoD...can't help you on that one. I bet it is more powerful than commercial PowerGel for rippin' a part rocks.

[Edited on 17-8-2005 by ((Blasta))]

acetone peroxide/AP/triacetone triperoxide/TATP/TCAP/peroxyacetone from 3% H2O2!

C6(NO2)5CH2CH(CH3)N(NO2)2 - 22-6-2019 at 14:03

So, the day before yesterday, I tried to make AP with 3% hydrogen peroxide disinfectant. I've heard of other people doing it before, they never gave their specific reaction conditions, and others saying it failed, and I wanted to know if it was possible. My first attempt failed, but the second I put about 70ml of disinfectant in a bottle, and left it in the freezer an hour until a bit of ice formed. Then I took it out, put 4ml acetone, and 7ml 10% hydrochloric acid and put it back in the freezer. My hope was that the low temperature (~-20C) would freeze some of the water out of solution, and make concentrated H2O2 in situ.

After 20Hrs, the mixture looked like a solid block of ice with a couple drops of free liquid. In reality, the block of ice was likely porous, with concentrated AP reaction mixture between the crystals. taking the bottle out of the freezer for an hour caused some of the ice to melt, although there was still frost forming on the outside of the bottle. The remaining ice rose to the top, while white particles settled to the bottom of the container. Then, before all the ice had melted, I added sodium bicarbonate until it stopped fizzing. Today, I filtered part of the mixture, and flame-tested the white sediment. Even when damp, it burned in a series of "puffs" of flame. After drying a piece slightly smaller than a rice grain, I put it on a piece of newspaper and touched it with a hot steel wire. It decomposed in a fraction of a second without burning the paper.

The yield from this procedure wasn't great, a gram or two I think compared to the theoretical 5+, but the material is definitely energetic. Just thought I'd share this method of using low concentration Hydrogen Peroxide.

MineMan - 22-6-2019 at 20:30

Interesting!

caterpillar - 22-6-2019 at 21:57

In our shops "hydroperite" is sold. It is the complex of hydrogen peroxide and urea. Add some acetone and a few drops of HCl. wait, wash and dry.

Rocinante - 24-6-2019 at 06:27

Interesting. More details like ratio, yield and procedure would be welcome.

TATP can be formed via air/light oxidation of diisopropyl ether, too.

caterpillar - 24-6-2019 at 11:34

Quote: Originally posted by Rocinante

Interesting. More details like ratio, yield and procedure would be welcome.

TATP can be formed via air/light oxidation of diisopropyl ether, too.

I used 30% H2O2. I'm talking about the experience of my friend. But the procedure is very simple. I think you should have an excess of H2O2. Make simple calculations. The aforementioned compound is sold as a big round tablet. You even do not need to smash it to pieces- only make it wet with acetone and drop HCl. Wait for one day, wash and dry.

acetone peroxide, AP, triacetone triperoxide, TATP, ,APEX, TCAP, peroxyacetone from 3% H2O2, more data.

C6(NO2)5CH2CH(CH3)N(NO2)2 - 5-12-2019 at 17:22

On November 23, 2019 I tried a somewhat more "systematic" test of the effect of freezing during an AP synthesis with diluted precursors. I Chilled containers of acetone, hydrogen peroxide (3% disinfectant) and muriatic acid (hardware store/technical grade, 31.45% HCl labled concentration) to under 5C. Then, I poured an identical mixture of the ingredients into three different 1 liter pete plastic bottles. I used 50gm (give or take 100mg) of peroxide solution, 2.56 gm (30mg tolerance) of acetone (assumed to be almost 100% concentration), and 1.73gm (30mg tolerance) of hydrochloric acid in each bottle. The amount of hydrogen peroxide was chosen arbitrarily, the amount of acetone was supposed to give a 1:1 molar ratio with the 1.5 gm of hydrogen peroxide already in solution, and the weight of hydrochloric acid was selected to give starting concentration of about 1% by weight HCl.

One bottle was left in a heated building, where the temperature was between 18 and 13C.

Another was left in a refrigerator where the temperature was about 3C.

The third was left in a freezer with an estimated temperature of -15 to -20 C.

Only I had access to the refrigerator/freezer, and I closed the bottles tightly and put them inside socks and then plastic bags to contain any leaks. I had previously tested one of the bottles and found that the cap began to leak profusely at a pressure of about 3 atmospheres. Fortunately no noticeable pressure formed in any of the bottles, and they stayed sealed.

On November 30th, 157 hours later, I checked the containers again. The "refrigerator" and "room temperature" specimens had no sign of precipitation, while the "freezer" one had just one big piece of ice and very little liquid. Almost all of the liquid was either frozen or absorbed into the ice block. I neutralized the clear liquids with baking soda and poured them down the sink. I left the "freezer" sample in the room to thaw.

After it thawed, but before it rose to room temperature, I checked it and found a lot of white precipitate at the bottom of the liquid. I added baking soda until it stopped releasing carbon dioxide. All of the fizzing caused gas bubbles to stick to the precipitate, bringing it to the surface. I diluted the mixture with water, filtered it, and washed the inside of the bottle with water to get the last bit of precipitate out.

The wet paste was scraped off the filter, and weighed at 2.7gm. After standing in open air for 12 hours, it weighed roughly .95 gm. after 11 more hours of drying, it still weighed .9gm, suggesting that drying was largely complete. The paste had still kept its shape from when it was wet, but I didn't try to break it up or check its consistency, for safety reasons.

a small (less than 20mg) piece of the product responded to flame with a very rapid deflagration, and no visible residue.

I may try to det. a few hundred mg. of my product, but that property is already well known and I'm fairly confident that it could work. The mechanism and optimisation of the reaction needs more attention.

The next test will be to re-wet the product, and take a ~100mg piece and test it with an acid, to confirm that it had little to no baking soda in it.

assuming that it is almost entirely AP, the yield was about .9gm out of a theoretical 3.25, or only about 28%. This is much better than with the shorter duration experiment, but is still fairly low.

When I filtered the mixture, the liquid that came through still had a lot of hydrogen peroxide in it, and bubbled as it went down the drain. This would explain the low yield. I suppose that a longer reaction period would help change this. Assuming I am right about freezing changing the concentration, It also might help to use less hydrochloric acid, since this lowers the freezing point and leads to a bigger more dilute volume that remains liquid. Acetone and hydrogen peroxide might do the same thing, but they get... precipitated as the reaction proceeds.

I am coming up with ideas of how to test my hypothesis about why freezing starts the reaction. I am thinking of trying a reaction at 3C with 10 or 20% hydrogen peroxide, and if that is successful we know the barrier at 3C is just low concentration. Then, assuming it is successful I could try the same at -20C but with a freezing point depressing salt. If it is still successful I would no that the salt had no effect on the reaction. Then I would try 3% at -20C, while using salt or some other inert freezing depressing agent to keep the whole solution liquid. If that reaction failed after the others were successful I would know that the main reason that freezing helps is that it "removes" water from the reaction and forms higher H2O2 concentrations in situ. If the reaction was successful with a completely liquid, salt protected 3% solution at -20C, that would mean some other factor was at play, perhaps there is a competing or AP-destroying reaction that happens at warmer temperatures.

[Edited on 6-12-2019 by C6(NO2)5CH2CH(CH3)N(NO2)2]

[Edited on 6-12-2019 by C6(NO2)5CH2CH(CH3)N(NO2)2]