bmays
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Acrylic acid
I have found patents (US8252960) which show acrolein is oxidized by air via a large variety of catalysts, although i wish to avoid this. How about
oxidation with dichromate or permanganate? Any ideas or tips how this might be done? I'm planning on simply adding potassium permanganate a small
amount of water should facilitate the oxidation, then distill. This stuff is horrendously acrid, i'm hoping this goes smoothly.
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CuReUS
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permanganate or dichromate will convert the double bond to a diol and may even cleave it
http://www.chemguide.co.uk/organicprops/alkenes/kmno4.html
better to do the pinnick oxidation instead - https://en.wikipedia.org/wiki/Pinnick_oxidation
also see this -http://pubs.acs.org/doi/abs/10.1021/jo00354a037
[Edited on 10-7-2016 by CuReUS]
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Ozone
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I should also warn you that acrolein is *nasty*. I've run into few lachrymators that are worse, and it can cause fatal pulmonary edema with very small
doses. Sartori profiles it as a war gas for good reason.
If you are going to mess with it, I hope you have a serious hood and are prepared with adequate PPE. I don't usually engage in nanny-grade fear
mongering, but I've worked with this one and...it was a memorable experience.
Good luck,
O3
-Anyone who never made a mistake never tried anything new.
--Albert Einstein
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careysub
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Acrolein is about as toxic as phosgene on brief exposure (3500 mg-min/m^3 Haber product), and causes cumulative injury as well on repeated exposure.
It made a terrible tear gas because although it is irritating, its toxic concentrations are the same as its lachrymatory concentrations (for most tear
gases there is an effective ratio of intolerable irritant concentration/hazardous concentration in the thousands, for acrolein it is less than 1:1).
7 mg/m^3 is threshold irritating, but can poison you fatally in about 8 hours
50 mg/m^3 is intolerable, but lethal in a 70 minute exposure
Threshold lethality, for sensitive individuals, will be less than this even.
So if you encounter any irritation from acrolein at all, you have not just an irritating concentration, but a hazardous-to-health one as well.
I remember a kid's chemistry manual that had as an experiment the heating of potassium hydrogen sulfate and a small amount of glycerin in a test tube,
and experiencing the irritating fumes produced. As conducted, no detectable harm would result, but still one cannot imagine such an experiment
appearing today.
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bmays
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Thanks Cureus. i think i will keep a cork in it until i get an HOCl scavenger and do some further reading. Maybe a weak solution of hydrogen peroxide.
Yes acrolein is atrocious. It gave my a headache yesterday. If i had known it was so bad i would have left it alone. How about potassium
peroxymonosulfate in methanol, to avoid azeotropes. Will the methyl ester be formed? Maybe stick to water.
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bmays
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Sorry Cureus your last link outlined the reaction conditions. I missed that yesterday.
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PHILOU Zrealone
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To avoid the use of accrolein...
Maybe start from CH2=CH-CO-CH3 (butenone) with NaOCl/NaOH (bleach)
CH2=CH-CO-CH3 + NaOCl/NaOH/H2O --> CH2=CH-CO2Na (aq) + HCCl3
Butenone could be done from aceton (propanone) and formaldehyde...via condensation crotonisation...
CH3-CO-CH3 + CH2=O -catalyst 1-> HO-CH2-CH2-CO-CH3 -catalyst 2-> CH2=CH-CO-CH3 + H2O
Formaldehyde must be in minority vs aceton otherwise you would get poly-hydroxymethylation ...
up to (HOCH2-)3C-CO-C(-CH2OH)3... and further reduction of the carbonyle into -CHOH- (thus yielding a nonane-heptol).
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
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careysub
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Thinking about acrolein a bit more - it is classed in the CW literature as a "toxic lachrymator".
Upon considering its true toxic characteristics, it occurs to me that this is a very misleading way of classifying it.
It should be considered a lethal lung injurant agent, but with exposure warning irritation.
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bmays
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Thanks PH Z. That seems like it would be a good route, if only acrylic acid wasn't miscible in water. I wonder if it could be salted out. MVK is
likely possible with a long reflux and excess of formaldehyde.
Hi careysub, yes pouring the acrolein from the flash into the bottle i got some fumes in my nose and eyes despite standing at arms length upwind and
it had me staggering, stings as bad as the hottest hot pepper but passes in 10 seconds. It would be hard to poison yourself without being in severe
pain. Turns out in the end most of what i made was somehow water anyways, thought i had everything sufficiently dry.... 5ml came over at about 140f,
40ml came over at 211f, and 15ml polymerized in the flask. I was experimenting with air in a hot copper tube and think i possibly made some acrylic
acid. Either that or it was glycerin, it didn't smell actually so i think it was burnt glycerin which distilled over. Nightmare tar like goop, took me
hours to clean and had to resort to chromic acid to finish it off. If i had $15 i would have thrown the china 250ml rbf in the garbage, but it has
served me well so i guess it deserves my tlc haha.
I don't have any hydroquinone, i was under the impression it took sodium hydroxide so polymerize acrylic acid into sodium polyacrylate. I guess i
better find some hydroquinone i might need it. I do believe what i was dealing with was polymerized glycerin though, not sure.
[Edited on 16-7-2016 by bmays]
[Edited on 16-7-2016 by bmays]
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CuReUS
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MVK is as toxic as acrolein 
| Quote: | | MVK is extremely hazardous upon inhalation causing coughing, wheezing and shortness of breath even at low concentrations. It will also readily cause
irritation of the skin, eyes, and mucous membranes. |
https://en.wikipedia.org/wiki/Methyl_vinyl_ketone#Safety
| Quote: | | I don't have any hydroquinone, i was under the impression it took sodium hydroxide so polymerize acrylic acid into sodium polyacrylate. I guess i
better find some hydroquinone i might need it. |
https://youtu.be/7oAcT4Duun4?t=677
as nile red's video showed,hydroquinone won't prevent polymerisation for very long.The best thing to do is to use the acrylic acid ASAP.
in case you still want to add an anti-oxidant,benzoquinone is a better choice (hydroquinone has to first convert to benzoquinone in the presence of
O2,only then it can act as radical scavenger,so why not use benzoquinone directly instead ?  )
[Edited on 16-7-2016 by CuReUS]
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