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Author: Subject: Iodoso & Iodoxy compounds
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[*] posted on 9-11-2005 at 08:50
Iodoso & Iodoxy compounds


Heres an interesting explosive group that I hadn't come across until recently. By oxidising an iodo compond where the iodine is attached to a carbon containing a doudle bond (=CH-I) or an aromatic ring containing one or more iodines its possible to produce the iodoso group (IO)and the iodoxy group (IO2). Both are explosive but the iodoxy group is more stable. The following is the method I used to produce iodoxybenzene.

1. Diazotisation of aniline to benzenediazonium chloride was done by dissolving aniline in 150ml water with 16.5g 32% hydrochloric acid. The temperature of this solution was brought down to ~0°C, to the chilled solution was injected with swirling 5g sodium nitrite in 15ml water. The solution was left for 10min at ~5°C to complete the diazotisation reaction.

<center><img src="http://www.sciencemadness.org/scipics/axt/iodoxy1.jpg"></center>

2. The diazonium group was replaced with iodine by addition of 10g potassium iodide in 20ml water. The swirled solution was then left to return to room temperature while bubbles of nitrogen were seen to be released. When the bubbling stopped a <a href="http://www.sciencemadness.org/scipics/axt/iodobenzene.jpg">dense black liquid</a> had seperated. Iodobenzene is clear and I'm not sure what the contaminants are but I pressed ahead knowing that aniline tends to make funky colours anyway (my aniline is already red). The crude iodobenzene was extracted with an eye dropper.

<center><img src="http://www.sciencemadness.org/scipics/axt/iodoxy2.jpg"></center>

3. References mention that the chlorination of the iodobenzene should be done in well dried chloroform with dry chlorine gas. I thought screw that and added a small quantity of wet iodobenzene to dichloromethane in a 100ml measuring cylinder, into this was run chlorine gas by the reaction of manganese dioxide with hydrochloric acid. No drying was used but it still worked and a decent yeild of <a href="http://www.sciencemadness.org/scipics/axt/iodobenzenedichloride.jpg">shimmering yellow crystals</a> of iodobenzene dichloride where able to be filtered from the DCM solution.

<center><img src="http://www.sciencemadness.org/scipics/axt/iodoxy3.jpg"></center>

4. Oxidation of the iodobenzene dichloride was done in 12.5% sodium hypochlorite solution (pool chlorinator). 1g of iodobenzene dichloride was added to 18g 12.5% sodium hydroxide and glacial 0.5g acetic acid was added to that. The solution was heated @ 65°C for one hour whereby the yellow crystals of iodobenzene dichloride turned white and the solution foamed with release of chlorine. The solution was cooled back to room temperature and filtered to recieve a good yeild of iodoxybenzene which was left on porous paper to dry.

<center><img src="http://www.sciencemadness.org/scipics/axt/iodoxy4.jpg"></center>

The iodoxybenzene is quite a feeble explosive as you would expect from such bad oxygen balance, which pops off when heated on a spoon but can be made to explode under confinement and detonate when struck with a hammer. There are some every interesting derivatives of these polyvalent iodo compounds that show far greater explosive qualities.

<center><img src="http://www.sciencemadness.org/scipics/axt/iodoxybenzene-deflag.jpg">
<a href="http://xmovies.webtop100.net/banners/iodoxybenzene.mpg">movie</a></center>

The iodoxy group is amphoteric (creates salts with both bases and acids) and the very sensitive perchlorate salt of iodoxybenzene has been isolated, a quote from ref 1, <i>"About a gram of the perchlorate was easily isolated, but it detonated with extreme violence while being spread, still damp, on a porous tile, causing personal injury, and so was not analysed."</i> Ref 1 also details the nitration of iodoxybenzene to m-nitroiodoxybenzene which is said to detonate at 213°C. Presumably you could also start with m-nitroaniline and carry out the same four steps that I did above.

Iodoalkenes are also very interesting starting points, diiodoxyethylene is known, and I expect its explosive properties live up to its acronym. I guess a route to diiodoxyethylene would be bubbling acetylene through iodine in ethanol. which is then oxidised. 1-chloro-2-iodoxyethylene (as 2-iodylvinyl chloride) is listed in Bretherick and said to explode violently on impact, friction or heating to 135°C.

Ref 4 shows some other very interesting derivatives, iodobenzene diacetate (from chlorination of iodobenzene in glacial acetic acid, I made some of this as well) when treated with aqueous perchloric acid greated a diphenylene-iodo-diperchlorate which can add to olefins to produce diperchlorate esters.

Lots of interesting stuff, pitty KI is a restricted chem here so I'm not sure if I can follow any of those up.

<font size="1"><u>References</u>
1) <a href="http://scimadpic.webtop100.net/banners/the_iodoxy_group.pdf">Masson, I <i>et. al</i>. J. Chem. Soc. 1935, 1669.</a>
2) <a href="http://scimadpic.webtop100.net/banners/organic_compounds_of_polyvalent_iodine_1943.pdf">Sandin, B. Chem. Rev. 1943. 32(3). 249-276.</a>
3) <a href="http://scimadpic.webtop100.net/banners/organic_polyvalent_iodine_compounds_1966.pdf">Banks, D. Chem. Rev. 1966. 66(3). 243-266.</a>
4) <a href="http://scimadpic.webtop100.net/banners/organic_polyvalent_iodine_compounds_1996.pdf">Stang, P & Zhdankin, V. Chem. Rev. (Review). 1996. 96(3). 1123-1178.</a>
5) <a href="http://scimadpic.webtop100.net/banners/ber_29_1567_1895.pdf">Willgerodt, C. Ber 29, pg 1567, 1895.</a>
6) <a href="http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=cv3p0485">Formo, M & Johnson, J. Organic Syntheses, Coll. Vol. 3, p.485 (1955); Vol. 22, p.72 (1942).</a>
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[*] posted on 9-11-2005 at 10:14


Very interesting!

I also want to make Iodobenzene myself, since I have the required chemicals.
I don't want to make the iodoxybenzene, but rather do something different with the iodobenzene, for example grignard reagent and the like.
The black coloration of the iodobenzene is caused by free iodine from oxidation of the iodide by nitrite. A wash with thiosulfate solution should remove the color.

My analytical grade aniline is red too, btw.

Can you tell me how you came across the information that Iodobenzene can be chlorinated and then oxidised?
I've never before heard of this reaction.
What kind of books mention such reactions?
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[*] posted on 9-11-2005 at 10:39


The chemical reviews articles above are quite lengthy (~100 pages all up) and detail the chlorination/oxidation. The most recent one contains a whole lot of other reactions and was the one I found first through pubs.acs.org looking for perchlorate addition products.

PATR 2700 also lists some iodoso/iodoxy products but is quite vague, usually only referencing to "beil". Also notes that only aromatic compounds are known, which is false.

The chlorination step for for iodoxy compounds can actually be left out, direct oxidation of iodobenzene to iodoxybenzene in caro's acid is said to be the best way in ref 1.
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[*] posted on 9-11-2005 at 10:57


I looked up Iodobenzene in Gattermann- Wieland and found the information about the polyvalent alkyl iodides. It was also stated that aromatics aren't the only iodo compounds that can be chlorinated.

"Iodobenzene dichloride" is actually Chloroiodophenyl chloride, C6H5ICl+ Cl-.
It's an ionic compound!

The preparation of Iodobenzene is also more complicated than your easy synthesis above, it requires basifying the reacted mixture in order to convert the by- product phenol into phenolate.
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[*] posted on 9-11-2005 at 11:12


Yes, I should have said to take no notice of the bonding situation around the iodine. It was drawn that way for convenience, and the references didnt come to any decisive answer.

The iodoso products are actually polymers when not in solution. Its argued <a href="http://www.arkat-usa.org/ark/journal/2003/I06_Varvoglis/AV-657A/AV-657A.asp">here</a> that the iodoxy compounds may be as well.

Orgsynth has a prep for <a href="http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=cv2p0351">iodobenzene</a> with the purifying steps, which I wasnt able to do anyway. Purification through chlorination seems to work for me.

<a href="http://www.acdlabs.com/iupac/nomenclature/79/r79_736.htm">Here</a> shows some of the structures (seems iodoxy is now refered to as iodyl). The other references would argue against these structures, the iodosyl structure was shown to be a polymer and the bond lengths in the iodyl group were shown to be more akin to the nitro group.

[Edited on 11-11-2005 by Axt]
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[*] posted on 13-12-2005 at 18:38


Attaching a couple references of interest, first gives the synthesis of the explosive iodylvinyl chloride, second the formation of perchlorate esters via alkyl iodides reacting with oxo-bridged iodane perchlorate (Ph-I(ClO4)-O-I(ClO4)-Ph) which no dought is explosive in itself.

From ref 4, pg 1141, first post. Regarding synthesis of the oxo-bridged iodanes "<i>These compounds are generally prepared by the reaction of PhI(OAc)2 or PhIO with the respective acids or anhydrides</i>". The acetate is simply prepared by iodobenzene + Cl2 in glacial acetic acid instead of DCM/chloroform.

And on same page "<i>Triflate 9 and perchlorate 166 are prepared from (diacetoxyiodo)benzene and aqueous perchloric or trifluoromethanesulfonic acid (eq 88).<sup>286</sup></i> " The russian article below is "ref 286".

The addition of oxo-bridged iodane diperchlorate to olefins producing diperchlorate esters is also noted on page 1141 of ref 4.

Heres synth of Iodylvinyl chloride and some other derivatives, in german.
<a href="http://scipic2.ft100.net/banners/iodylvinyl chloride.pdf">Thiele, J. et al., Ann., 1909, 369, 131</a>

This is an english translation of a russian article, I think a lot was cut out regarding the diacetate -> iodoperchlorate reaction :mad: Only briefly talks about the iodoalkane -> perchlorate ester.
<a href="http://scipic2.ft100.net/banners/aryl-iodoso-derivatives.pdf">Zefirov, N. S.; Koz’min, A. S.; Zhdankin, V. V. Izv. AN SSSR, Ser. Khim. 1983, 1682.</a>

[Edited on 14-12-2005 by Axt]
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biggrin.gif posted on 14-12-2005 at 12:24


Quote:
Originally posted by Axt

Iodoalkenes are also very interesting starting points, diiodoxyethylene is known, and I expect its explosive properties live up to its acronym. I guess a route to diiodoxyethylene would be bubbling acetylene through iodine in ethanol. which is then oxidised. 1-chloro-2-iodoxyethylene (as 2-iodylvinyl chloride) is listed in Bretherick and said to explode violently on impact, friction or heating to 135°C.



Bubbling acethylene through I2 in Ethanol will provide more certainly diiodoacethylene...wich is also explosive ;):P:D...
But no easy way to diiodethylene or diiodylethylene that way.:(


All your good stuf and work has revided my old demon, a quest hidden somewhere in my brain...and what I expose here under will no doubt give a little wood to your fire :cool::cool::cool:

:D:cool::):P;):D:cool::):P;):D:cool::):P;):D:cool::):P;)
Maybe as the oxydation remains on the periphery of the molecule this would be a convenient route to diiodylacethylene...
For sure to handle with a great care and only in tinymini quantities...
H-C#C-H + I2 --> I-C#C-I + 2HI
I-C#C-I + (O) -?-> O2I-C#C-IO2
Note that dinitroacetylene brother has proven to be extremely difficult to obtain (not yet obtained despite a lot of work for decades)... It is the monomer of a powerful trimer explosive called Hexanitrobenzene (VOD near 10 km/s but water sensitive)...
-Note the perfect OB of diiodylacethylene....
O2I-C#C-IO2 --> 2CO2 + I2(g) + heat
-Maybe it may trimerise into HIB...for sure outperforming HNB?
-the sum of 3 explosophoric groups will account for a high unstability...
-The presence of I will account for a very high density...
-Triple bond will account for high energy output.

I wonder if by a mere chance you have shock sensitivity datas and density data of the iodosyl- and iodyl- (nitro) benzene.

As a side note comparison between nitrobenzene and iodyl benzene show that despite equivalent OB iodyl is more explosive...what would you expect as I have mentionned a long time ago on alt.engr.explosive (I think?) of a diiodyl and triiodyl benzene brothers of dinitro and trinitrobenzene...

Also hexanitrosylbenzene...obtained by the spontaneous decomposition (accelerated by moderate heating) from 1.3.5-triazido,2.4.6-trinitrobenzene leaves a stabler compound wich has the sensitivity and the explosive power of Tetryl...
Thus as hexanitrosobenzene is stabler than hexanitrobenzene, one might consider if hexaiodylbenzene is a no-go to investigate hexaiodosylbenzene.

:D:cool::):P;):D:cool::):P;):D:cool::):P;):D:cool::):P;)




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[*] posted on 14-12-2005 at 13:31


Just out of curiosity,

Wouldn't this be correct?

C<sub>6</sub>H<sub>6</sub> + I2 -AlI<sub>3</sub>-> C<sub>6</sub>H<sub>5</sub>I + HI



[Edited on Wed/Dec/2005 by Nerro]
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[*] posted on 14-12-2005 at 19:32


I HIGHLY doubt the hypothetical (at this point) HIB would not outperform HNB, as HNB has a VERY high energy content, density etc. While I do not doubt it would be powerful and extremely interesting, I think it would fall short of HNB.

Although the iodoxy compounds are more explosive than their nitro versions, I think this has to do with the fact they "fall apart" easier, rather than actually having more power. I think that when it comes to much higher nitrated compounds (ie HNB) the advantage the iodoxy compounds gain from exploding easier will completely dissappear and be replaced by a lower energy content from the presence of very heavy iodine atoms in the molecules.

Dinitroacetylene is the monomer of many explosives, including octanitrocubane, which is why I think there is alot of work on it, cheap octanitrocubane would be a very useful thing indeed :D


However, I think that the diiodoxyacetylene compound does have a good amount of promise assuming that you can make it. Both steps to oxidize the iodide to iodoxy will destroy the triple C#C bond.

Also, if I had triazidotrinitrobenzene (which I hope to have soon) I would keep it as it is, after all it is an initiator six times stronger than lead azide, less sensitive than nitroglycerin and about as powerful as RDX. Also, it wasn't hexanitroslbenzene, I think it was a furazan.... someone would have to check what it was. But I remember it is described as hexanitrosylbenzene in some (quite a few) books when it has now been shown to not be a nitroso compound.
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[*] posted on 14-12-2005 at 22:36


Quote:
Bubbling acethylene through I2 in Ethanol will provide more certainly diiodoacethylene...wich is also explosive ... But no easy way to diiodethylene or diiodylethylene that way.


I'm a step ahead of you there Philou, <a href="http://www.sciencemadness.org/talk/viewthread.php?tid=4915">diiodoacetylene</a>. Heres an extract that gives the syth of diiodoethylene, the "Kaufmann" reference that should go into more detail is H. P. Kaufmann. Ber., 55B, 249-267 (1922).

<i>"The trans-diiodoethylene was prepared by passing acetylene into a solution of iodine in alcohol as directed by Kaufmann.* The commercial tank acetylene was purified by water and sulfuric acid according to the method of Reichert and Nie~wland.~ The crystals were filtered and repeatedly recrystallized from 95'7, ethyl alcohol. After its final crystallization, the product melted at 72.573". Experiments showed that iodine neither added to this trans-diiodoethylene nor was liberated."</i> </i> JACS, <b>67</b>, 1319 (1945)

This was tried, but the addition was very slow. Its probably only feasable through tank acetylene. The oxidation to diiodoxyethylene was done with perbenzoic acid, damned if I can find the reference to it now though..

Quote:
I wonder if by a mere chance you have shock sensitivity datas and density data of the iodosyl- and iodyl- (nitro) benzene.


Iodoxybenzene isn't overly sensitive to impact, a quote from ref 2 in first post.

<i>"Because of their explosive properties, iodoxy compounds should be heated with extreme care. Morrison and Legge (51) have done work on the impact sensitivity of iodoxybenzene. They have found that it explodes on an anvil when struck with a hammer and that it undergoes decomposition when hit by a 500-g. weight falling through a distance of 100 cm. It was also found that its power in the sand-crushing test was very low."</i>

I did try to form diiodoxybenzene through diazotisation of phenylenediamine, but a very dirty crystaline product was obtained which looked and smelt a lot like iodine. Diiodoxybenzene should be considerably more "explosive" then iodoxybenzene, considering dinitrobenzene is a reasonably powerful explosive where mononitrobenzene has little to no explosive properties. It is listed in PATR 2700 vol 7, pg I 125. I quote: <i>"white tablets, explodes very violently at 261° or on impact; v sl sol in w or glac HAc. Prepd by heating m-diiodosobenzene with steam."</i>

Quote:
it wasn't hexanitroslbenzene, I think it was a furazan....


Regarding hexaiodosylbenzene, if you look at the <a href="http://www.its.caltech.edu/~dmacgrp/grpmtgs/2003/SL-iodine.pdf">structure of (poly)iodosylbenzene</a> it looks most likely that hexaiodosylbenzene would take on the same structure as its nitrogen analogue:

<center><img src="http://www.sciencemadness.org/scipics/axt/hexaiodosylbenzene.jpg"></center>

[Edited on 15-12-2005 by Axt]
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[*] posted on 16-12-2005 at 18:00


Good stuf Axt as usual :)

I wonder if trans diiodoxylethylene exists, if the iodyl brother of FOX (diaminodinitroethylene) might exist...as I'm also convinced there is a correlation between the -IO2 and -NO2...I have little doubt if needed a amino group might not help stabilising the Iodyl...in the case of polyiodylated compounds via a furazan like ring...

Also too bad there are no refs about cis-diiodyl and gem diiodylethene :(


Which phenylene diamine did you tried?
Ortho, meta or para?




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[*] posted on 16-12-2005 at 20:03


Quote:
Originally posted by Chris The Great
I HIGHLY doubt the hypothetical (at this point) HIB would not outperform HNB, as HNB has a VERY high energy content, density etc. While I do not doubt it would be powerful and extremely interesting, I think it would fall short of HNB.


Don't be so certain of this...in the explosive field every increase of 0.1g/ccm allow and increase of VOD of about 350m/s...Density of HNB is close to 2.1...Density of HIB could easily be higher than 3...density of diiodylethene would give a good idea of the density increase generated by two IO2 groups...and increase of VOD of 3500m/s is quite a big jump.

Quote:
Originally posted by Chris The Great
Although the iodoxy compounds are more explosive than their nitro versions, I think this has to do with the fact they "fall apart" easier, rather than actually having more power. I think that when it comes to much higher nitrated compounds (ie HNB) the advantage the iodoxy compounds gain from exploding easier will completely dissappear and be replaced by a lower energy content from the presence of very heavy iodine atoms in the molecules.

I'm not sure of this...most of the references of Axt list decomposition temperatures between 130-230°C ... So it might prove to be quite stable.
Also decomposition temperature is correlated to the shock sensitivity/Activation Energy not to the VOD.

Last but not least... indeed very dense explosive do not perform better on all aspects...but remember that most tests are based on weight...it would be an excellent idea to have also volumic tests or mol rated tests...I think it might change quite a lot the idea some person have about the power of an explosive...

1)Imagine an explosive A with a Lead block test 675 ccm/10g (d=1) and an explosive B which LBT is 300 ccm/10g (d=4)...

Which one is the best?

2)If explosive A has a density of 1, it means that LBT was 675 ccm/10ccm explosive!
If explosive B has a density of 4 then LBT was 300 ccm/2.5ccm explosive!

Wich one is the best?

3)Now imagine we take the same volume of the two...
A: 675 ccm/10 ccm
B: 300 ccm/2.5 ccm --> 1200 ccm/10ccm

Which one is the best?

Note that I have used a linear extrapolation but the effective rule about power of an explosive charge is based on the dubbling of its mass is quadratic... The thruth is thus comprised between 1200 ccm/10ccm and 2100ccm/10ccm.
From this simple demonstration you see that yes A perfoms half way better on the weight basis, but that it pulverises the lead block at an equal volume.

So weight is a real concern about flying devices...but no concern about contact or land explosive,...a land mine is the same as another landmine....but what if in the same volume you get 3 times more power...


Quote:
Originally posted by Chris The Great
However, I think that the diiodoxyacetylene compound does have a good amount of promise assuming that you can make it. Both steps to oxidize the iodide to iodoxy will destroy the triple C#C bond.

About the triple bond being oxydised during the proces to change diiodoacethylene into diiodylacethylene...I honnestly don't know...but you must not be too fast to conclude...
You must remember that triple bond isn't directly oxydised by KMnO4, by HNO3, by O2 or by H2O2...sensitivity of acethylene is mostly based on activity of H(+) or other (+)catalyst that fixes or alterates pi bondages...by chance most oxydants are anionic :)...
Also the proces involve mostly low temperatures...thus...if you don't push it to far...

Quote:
Originally posted by Chris The Great
Also, if I had triazidotrinitrobenzene (which I hope to have soon) I would keep it as it is, after all it is an initiator six times stronger than lead azide, less sensitive than nitroglycerin and about as powerful as RDX. Also, it wasn't hexanitroslbenzene, I think it was a furazan.... someone would have to check what it was. But I remember it is described as hexanitrosylbenzene in some (quite a few) books when it has now been shown to not be a nitroso compound.

Furazane ringing ... if I remember accounts for the astonishing resistance of TATB towards heat. See attachement to understand the difference between dehydrated TATB and deazotised TATNB...

I agree TATNB is interesting but stil it has to be pressed to a high density to give the best results!

Hexanitrosylbenzene is a potent precursor of hexadecaazatriphenylene...C6N16...an aromatic molecule

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[*] posted on 17-12-2005 at 13:53


Oh, I never implied that the hexaiodoxy compound would not be powerful, what I was trying to say is that I think it would be like mercury fulminate or something, in that the large, heavy atom dilutes the explosive effect and so VoD, Det pressure, brisance etc are low despite a very high density. It is still explosive but it does not have great disruptive power or blast power from all the mercury it contains, and I think the same thing would happen with the hexaiodoxy compound except that iodine would be the dilutant.

The problem with your hypothetical molecule is that those nitrogen rings do form easily and only exist on one molecule. Attempts to introduce even one of those rings on a benzene molecule has resulted in immediate decomposition even at dry ice temperatures. So despite the fact that it looks stable on paper, in real life it is very different (unfortunately :( )
The other problem is that it does not from hexanitrosylbezene, but rather an oxidized version of the TATB molecule, with an additional oxygen on every second ntirogen. I checked Urbanski (vol 3, pg 193) and it gives the name of benzotrifuroxane and also a structural diagram.
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[*] posted on 19-12-2005 at 04:09


Mhmmmmm :mad: I was unclear...

From this simple demonstration you see that yes A perfoms half way better on the weight basis, but that B pulverises the lead block at an equal volume.

[Edited on 19-12-2005 by PHILOU Zrealone]




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[*] posted on 19-12-2005 at 04:27


Quote:
Originally posted by Chris The Great
Oh, I never implied that the hexaiodoxy compound would not be powerful, what I was trying to say is that I think it would be like mercury fulminate or something, in that the large, heavy atom dilutes the explosive effect and so VoD, Det pressure, brisance etc are low despite a very high density. It is still explosive but it does not have great disruptive power or blast power from all the mercury it contains, and I think the same thing would happen with the hexaiodoxy compound except that iodine would be the dilutant.

The problem with your hypothetical molecule is that those nitrogen rings do form easily and only exist on one molecule. Attempts to introduce even one of those rings on a benzene molecule has resulted in immediate decomposition even at dry ice temperatures. So despite the fact that it looks stable on paper, in real life it is very different (unfortunately :( )
The other problem is that it does not from hexanitrosylbezene, but rather an oxidized version of the TATB molecule, with an additional oxygen on every second ntirogen. I checked Urbanski (vol 3, pg 193) and it gives the name of benzotrifuroxane and also a structural diagram.

:D
True that for Hg fulminate Hg...dilutes the effect...but it is relatively inert...here iodine is an oxygen carrier...
1)To test you assumption...experiment is quite simple...we simply have to compare NH4NO3 with NH4ClO3 and with NH4IO3...

NH4IO3 is stabler than NH4ClO3 on handling...NH4ClO3 has been isolated but is dangerous to keep or make in large amounts so play with it in tiny quantities!

2)Compare explosive properties of meta dinitrobenzene with meta nitroiodylbenzene and meta diiodylbenzene...
3)Compare TNB with 1 iodyl, 3.5-dintro benzene...
4)Compare TNP with ortho iodyl, 4.6-dintrophenol...

At the end of those tests the truth about iodyl vs nitro will be shown...
:P:P:P




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[*] posted on 19-12-2005 at 05:37


Quote:
Originally posted by PHILOU Zrealone
I wonder if trans diiodoxylethylene exists


Theres one sentence devoted to diiodoxyethylene on page 254 of ref 3 first post. Quote <i>"Boeseken and Schneider (5, 6) used perbenzoic acid in chloroform as the oxidizing agent and thus obtained the o-diiodoxybenzene and diiodoxyethylene from the corresponding diiodo compounds."</i>.

Quote:
Which phenylene diamine did you tried?
Ortho, meta or para?


meta.

Diazotisation was done with large excess of HCl (needed to stabalise bis-diazonium salts) addition of KI produced a lot of bubbling like it should, but no precipitate (m-diiodobenzene is a solid). On standing some crystals formed on bottom looking like iodine. These were dissolved in glacial acetic acid and chlorine passed through it, a yellow precipitate formed.

I forget what I actually did with this precip. It was done before the monoiodobenzene. I think I tried to react the supposed tetraacetate with NaOH to form diiodosobenzene but failed. Whatever the case, the supposed m-diiodobenzene was very ugly and dirty looking, not a nice precipitate at all.

[Edited on 19-12-2005 by Axt]
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[*] posted on 19-12-2005 at 06:13


Quote:
Originally posted by Axt
Quote:
Originally posted by PHILOU Zrealone
I wonder if trans diiodoxylethylene exists


Theres one sentence devoted to diiodoxyethylene on page 254 of ref 3 first post. Quote <i>"Boeseken and Schneider (5, 6) used perbenzoic acid in chloroform as the oxidizing agent and thus obtained the o-diiodoxybenzene and diiodoxyethylene from the corresponding diiodo compounds."</i>.

-I know I did read all the good stuf of you :)

The complete sentence was:
I wonder if trans diiodoxylethylene (does) exists, if the iodyl brother of FOX (diaminodinitroethylene) might exist...
So I meaned has someone eard about diaminodiiodylethene...?

Sorry again i forgot the "does"... ;)




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[*] posted on 21-12-2005 at 06:01


Quote:
Originally posted by PHILOU Zrealone
So I meaned has someone eard about diaminodiiodylethene...?


Nope. But heres a simple way to get to I2C=CI2, so one can test to see if two iodyl groups off the same carbon can be done, I've seen no reference to it.

<i>The tetraiodoethylene used in these experiments was prepared from diiodoacetylene by treatment in petroleum ether with iodine in slight excess. The tetraiodoethylene precipitated as golden scales and after filtering and drying was dissolved in anhydrous ether. A saturated solution of tetraiodoethylene in anhydrous ether at 19° contains 47 g. to the liter. Such an ether solution was used as the basis for the calculation of the quantities used.</i> J. Am. Chem. Soc.; 1912; 34(3); 290-295.

I made iodylbenzene again, measuring useful yields (that after bottling).

aniline -> iodobenzene went to 85% yield
iodobenzene -> iodobenzene dichloride went to 50% (maybe thats why they specify <i>dryness</i> of reactants.
iodobenzenedichloride -> iodylbenzene was 0.5g from 2.5g

The low yield was doe to washing it with an extra 100ml water which dissolved some product but washed out any NaCl, this product is considerably more "explosive" then the last flashing with a thump when touched with the flame of a match, still a little slower then blackpowder.

Into the filtrate was added some perchloric acid, resulting in a fluffy precipitate of supposed iodylbenzene perchlorate, shown below.

<center><img src="http://www.sciencemadness.org/scipics/axt/iodylbenzene-perchlorate.jpg"></center>

I'm going away tomorrow, over christmas, so I'll have to leave that with the hope that on my return it hasn't formed into some super crystal of doom.
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[*] posted on 3-7-2006 at 14:39


What happened to/with the perchlorate crystals Axt?

I gave the peracetic acid method on orgsyn for the prep of iodoxybenzene a try today. I just modified it for home made 8.6% peracetic and for m-nitroiodobenzene instead. It did not end up working, likely because the peracetic was too dilute.

oops, forgot to chill, so I did get some m-nitroiodoxybenzene. However there was much iodo contaminating/remaining, so a future try must have stirring coninue for much longer if such dilute peracetic is employed.

[Edited on 3-7-2006 by rogue chemist]




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[*] posted on 4-7-2006 at 23:36


Quote:
Originally posted by rogue chemist
What happened to/with the perchlorate crystals Axt?


By the time I got home there I was only left with a small quantity of black liquid.. somehow it seems to have been reduced back to iodobenzene then darkened. It was left outside in sun. So I can't confirm that it was the perchlorate, it looks like there is a large precipitate in the picture but it was very fluffy so there wasnt much of it there.

How'd you get to m-nitroiodobenzene? Were you able to check explosive props for the iodoxy precipitate?

Diaminofurazan would be an interesting precursor to some iodoxy compounds too I think.

[Edited on 5-7-2006 by Axt]
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[*] posted on 11-1-2009 at 00:56


This is the direct oxidation of iodobenzene to iodylbenzene using K2S2O8 + H2SO4, taken from Bamberger & Hill "Directe Oxydation von Jodarylen" Ber. 33, 533-536 (1900).

Can anyone translate?

iodo-iodylbenzene.jpg - 89kB
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[*] posted on 11-1-2009 at 09:11


The oxidizing solution - consisting of 56 g potassium persulfate, 60g conc. H2SO4 and 90g ice contains - as shown by the titration with Mohr's Salt- in 100 ccm 2.06g active oxygen. After 13.1 g iodobenzene was agitated thoroughly with 99 ccm of that liquid on the machine after 2.5 hrs, it changed nearly entierly into a thick, shining needle-mush consisting of iodylbenzene. The product which was then washed with water and dried in a dessicator to constant weight contained 98.97% iodylbenzene, since:

1. 0.2896g liberated so much iodine out of KI, as to what corresponds to 48.37 ccm 1/10-norm. sodium thiosulfate (0.03869g O).


Then the rest is also just verifiying the product by analysis, it crystallized from cooling water in white, silk-glancing needles with deflagration at 238°C. Beilstein lists it as exploding at 236-7°C. If you look in B. 29, 1571, 1572 then there is a procedure from Willgerodt using iodobenzene and hypochlorous acid or NaOH with Br2.

Btw, Beilstein has a whole bunch of these iodoso- and iodyl- compounds listed (in Band V, 4. Auflage). Some which caught my attention from benzene: Iodosobenzene deriative: C6H5.ICrO4. Yell. ppt. Turns dark-red on drying, expl. at 66-67°C. Quite a few with other halogens together, e.g. m-chloro-iodylbenzene (C6H4Cl.IO2, expl. at 233°C). 1,3-Diiodylbenzene (C6H4(IO2)2), barely sol. in H2O, GAA, expl. very violently at 261°C or by impact. o-Iodylnitrobenzene (O2N.C6H4.IO2) expl. violently at 210°C; etc.

Then even the higher hydrocarbon analogues still have explosive properties. Like m-iodyltoluene (CH3.C6H4.IO2) which expl. at 220°C, or deflagrates at 214-221°C according to that Berichte paper above. Even the acetate of 4-iodoso-3-nitrotoluene (O2N.C6H3(CH3).I(C2H3O2)2) expl. at 200°C. Xylene: asymm. iodyl-m-xylene ((CH3)2C6H3.IO2), expl. at 180 or 195°C.

[Edited on 11-1-2009 by Formatik]
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[*] posted on 14-9-2011 at 17:41


Axt In your starting post your link 'shimmering yellow crystals' will not work. However I can view the actual pic at :

http://www.sciencemadness.org/scipics/axt/iodobenzenedichlor...

Also 'dense black liquid :

http://www.sciencemadness.org/scipics/axt/iodobenzene.jpg

iodoxybenzene.mpg is gone from the server also after correcting the link.

and others:

http://www.arkat-usa.org/ark/journal/2003/I06_Varvoglis/AV-6...

http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=cv2...

http://www.acdlabs.com/iupac/nomenclature/79/r79_736.htm



[Edited on 9-15-2011 by IrC]




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