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Author: Subject: Organic peroxides
PHILOU Zrealone
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[*] posted on 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!
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[*] posted on 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.
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PHILOU Zrealone
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[*] posted on 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
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[*] posted on 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.
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[*] posted on 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!

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[*] posted on 20-8-2002 at 08:48
paraldehyde triperoxide


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




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[*] posted on 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)




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[*] posted on 24-8-2002 at 02:41
Thanks


This is similar to the process I had seen, and overcomes the problem of excess oxidation of the CH2O, thanks a lot for posting.
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[*] posted on 26-5-2003 at 10:12
problems with AP synth


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!



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[*] posted on 26-5-2003 at 16:31
sorry


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.
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[*] posted on 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




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[*] posted on 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]




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[*] posted on 26-5-2003 at 20:06
Formaldehyde


I've seen CH<sub>2</sub>O produced by a rather powerful spark underwater using graphite electrodes.
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madscientist
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[*] posted on 26-5-2003 at 20:23


That's the bicyclic form of cyclohexanone peroxide.



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PHILOU Zrealone
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smile.gif posted on 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!




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biggrin.gif posted on 4-6-2003 at 04:41


And of course... nitro and dinitrocyclohexanone peroxydes



PH Z (PHILOU Zrealone)

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[*] posted on 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>
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[*] posted on 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.



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cool.gif posted on 4-9-2003 at 18:39
more ...


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:
H<sub>2</sub>SO<sub>4</sub> + HOOCCH<sub>2</sub>C(COOH)(OH)CH<sub>2</sub>COOH => HOOCCH<sub>2</sub>COCH<sub>2</sub>COOH + 2H<sub>2</sub>O + SO<sub>2</sub> + CO<sub>2</sub>
add the mix drop by drop to ice cold (preferably conc) H<sub>2</sub>O<sub>2</sub> <b>hoping</b> to get di/tri/..mer of <b>per</b>acetone dicarboxylic acid peroxide. a cyclic dimer:
<img src="http://www.angelfire.com/rnb/pjff/padcp.gif">
C<sub>10</sub>H<sub>12</sub>O<sub>16</sub> => 10CO + 6H<sub>2</sub>O
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)]




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[*] posted on 7-9-2003 at 04:40


does someone have some information about benzoyl peroxide ? i found some info on xinventions forum ... but nothing else ...
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[*] posted on 7-9-2003 at 08:50
benzoyl peroxide


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]
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[*] posted on 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.
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[*] posted on 30-11-2003 at 21:07


Krypton:
<blockquote>quote:<hr>Here some knowledge to a old new synthesis<BR>by me to a meltable and thermic insensitive<BR>dicyclic peroxide.<BR><BR><a href="http://www.sciencemadness.org/scipics/dicycloperoxide.JPG" target=_blank>dicycloperoxide</a><BR><BR>It`s a fine powder, chemical stable and <BR>insensitive against shock and high temperatures <BR>with a sweet odour.<BR><BR>mp ~100 C <BR>dc &gt;350 C, (ignition) <BR>ev ~ 7500 m/s<hr></blockquote>cyclohexanone peroxide is<b>n't</b> C<sub>6</sub>H<sub>10</sub><(OO)2>C<sub>6</sub>H<sub>10</sub> it is<img src="http://www.angelfire.com/rnb/pjff/chnp.gif">
from the condensed chemical dictionary:
<b>cyclohexanone peroxide</b>&nbsp;&nbsp;(1-hydroperoxycyclohexyl
&nbsp;&nbsp;1-hydroxycyclohexyl peroxide)
&nbsp;&nbsp;C<sub>6</sub>H<sub>10</sub>(OOH)OOC<sub>6</sub>H<sub>10</sub>OH.
&nbsp;Properties: Grayish paste; insoluble in water; soluble
&nbsp;&nbsp;in most organic solvents.
&nbsp;Hazard: Dangerous fire risk in contact with organic
&nbsp;&nbsp;materials. Strong oxidizing agent.
&nbsp;Shipping regulations: (Rail) (not over 50%) Organic
&nbsp;&nbsp;Peroxide label; (50-85% Organic Peroxide label.
&nbsp;&nbsp;Not acceptable passenger. (Air) (not over 50%)
&nbsp;&nbsp;Organic Peroxide label;(50-85%) Organic Peroxide
&nbsp;&nbsp;lable. Not acceptable passenger. (Over 85%) Not
&nbsp;&nbsp;acceptable.

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




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[*] posted on 13-12-2003 at 22:09
methyl isobutyl ketone


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!



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[*] posted on 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 ! :)
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