[AlphaScent]

Hey All,

I did a trial reaction last night using TEMPO to go from (Z)-11-hexadecen-1-ol to the aldehyde.  It is done in air and O2 is the terminal oxidant.  When I tried to dissolve my alcohol in acetonitrile, as the experimental from my paper called for, it was more of a heterogeneous mixture.  What is the next polar aprotic solvent you would try?  I am thinking acetone or THF?  I suggest these two solvents because water is a o solvent. 2:1; acetonitrile:water.

Attached is the paper I am going off of. 

[Adamcp898]

Hadn't time to go through the paper but I'd imagine you'll have trouble getting a long chained alcohol like that to dissolve in polar solvents, particularly one miscible with water, and even if you do, adding water could cause it to come back out of solution again.

[AlphaScent]

My thoughts exactly, the paper says that the aliphatic oxidations dont go to completion after 24 hours.  Mine went to 35% completion.  I am just wondering if the next move is to dial back the water or try a different solvent. 

[Adamcp898]

My thoughts exactly, the paper says that the aliphatic oxidations dont go to completion after 24 hours.  Mine went to 35% completion.  I am just wondering if the next move is to dial back the water or try a different solvent.

Oh so it did actually work. I thought you were talking about it in terms of it had been a complete failure.

Well like I said I haven't had time to look at the paper (I'm procrastinating enough as it is  ) but yes perhaps try doing it in just ACN, they could've been adding the water to try and emphasise the ''greenness'' of their chemistry. Or just wait for a response from someone who has an opportunity to consider it more!

[discodermolide]

Use bleach and TEMPO in water dichloromethane and stirr well.
O₂ is bas under oxidising conditions with acetone or tHF (peroxide formation = explosion danger)

[AlphaScent]

Thanks Adam,

I am thinking it helps with the Copper (II) Bromide solvation. 

It is  5 mol % of Cu(II)Br2, TEMPO, KOH, 2,2'-bipyridine

Then the alcohol dissolved in ACN:H2O.  Stir over night.

They oxidize Octan-1-ol to 95% with a bit of heat (40) and 7.5% TEMPO.  I just added more TEMPO and am putting a bit of heat into it.  Ill post again tomorrow about the results.

[AlphaScent]

Disco,

I must agree with you on the danger.  I will not try it.

What would the ratio of reagents be?  What % TEMPO and bleach?

I will surely try it.

[discodermolide]

Remember I sent you a copy of my papers, it's in the experimental of part 1

[AlphaScent]

I dont have any of the potassium bromide, though.  Can I do without it?  I thought the sodium hypochlorite reacts to for the hypobromite? 

[discodermolide]

No you need KBr, as it forms K bromate which is the oxidiser.
Perhaps you can get away with NaBr.