Sciencemadness Discussion Board

triphenylphosphine oxide preparation

mackolol - 20-5-2018 at 00:29

Hi, I want to make triphenylphosphine oxide from TPP. I know that TPP gets easily oxidized even by atmospheric oxygen, but i can't find any synthesis on internet except for the appel reaction in which its a byproduct. Can anyone post here synthesis of TPP oxide from TPP?

unionised - 20-5-2018 at 01:11

TPP is used as a reagent for measuring H2O2 in air.
You can make TPPO by oxidising TPP with H2O2 in acetonitrile - other solvents might work too, but that's the one I used.
I can't see why ethanol or methanol wouldn't work.

https://pubs.acs.org/doi/abs/10.1021/ac9701750?src=recsys&am...

Texium - 20-5-2018 at 18:43

Any solvent that can dissolve TPP should work, and if it doesn't dissolve TPPO as well it would work even better. You could probably even bubble air into it and have the TPPO simply precipitate out.

I run a lot of reactions that produce TPPO as a byproduct where it is thrown out as waste. I'm curious, what use do you have for it?

mackolol - 21-5-2018 at 08:02

I want to make green triboluminescent compound which is Mn(Ph3PO)2Br2 complex

Fery - 7-1-2026 at 11:11

Too late reply but I found the synthesis here, dissolving triphenylphosphine in acetone and bubbling air through it, no catalyst used:
https://www.youtube.com/watch?v=dJ6sP5Yzph0
a scientific paper about the oxidation using iron complexes catalysts FeBr3 and Fe(SCN)3 optimal catalyst ratio 1:50, time 10-15 hours using pure oxygen:
https://annas-archive.se/scidb/10.1135/cccc19830254/

Attachment: cccc19830254.pdf (773kB)
This file has been downloaded 13 times

video with synthesis of the triboluminiscent compound and its luminscence:
https://www.youtube.com/watch?v=M042e-yd4uU
does someone know why they used MnBr2 ?
would MnCl2 work too? just slightly different color with spectrum shifted by few nm?

I have triphenylphosphine and triphenylphosphine sulfide (I just do not have the desired oxide) - does someone know whether the sulfide is also suitable for the luminiscence?
I don't have the oxide, but have everything to prepare it (from the triphenylphosphine in acetonitrile solvent using some iron catalyst as described in the attached document).
I do not have MnBr2 but it could be prepared from metallic Mn (I have commercial 99,9% Mn produced electrolytically) and HBr or Br2 (I have both of them analytical grade purity)
I certainly have few packages of MnSO4. I very likely do not have MnCl2 but it could be prepared from MnO2 + 4 HCl (I have both of them analytical grade purity).

I have bought the phosphine because it is good way to purify thionyl chloride:
Quote:
Thionyl chloride is conveniently obtained in a high state of purity by atmospheric distillation of commercial material over 10 weight per cent. of triphenyl phosphite.

https://pubs.rsc.org/en/content/articlelanding/1967/j1/j1967...
https://doi.org/10.1039/J19670000036

SOCl2 + triphenylphosphine could be also used for deoxygenation of sulfoxides to sulfides:
https://pubs.acs.org/doi/10.1021/jo4008157

These were 2 reasons why I have bought the useful thiphenylphosphine in bulk (and there was also one package of its sulfide, just not the oxide). Now the luminiscence is third interesting usage of this reagent.