allchemy
Harmless
Posts: 4
Registered: 23-12-2011
Member Is Offline
Mood: No Mood
|
|
A puzzle from the Mitsunobu reaction
My work is to synthesis a ether by Mitsunobu reaction(triphenylphosphine and DIAD mole ratio is about 1:1),in the work up procedure
,triphenylphosphine oxide and diisopropyl hydrazodicarboxylate is precipitated from the solution , triphenylphosphine oxide content is > 70% and
diisopropyl hydrazodicarboxylate is 23% by GC analysis from this precipitates, in the filtrate, triphenylphosphine oxide content is between 10%-12%
and diisopropyl hydrazodicarboxylate is < 4% and triphenylphosphine is about 5%.The total triphenylphosphine oxide is far outweigh diisopropyl
hydrazodicarboxylate ,why is not approach to 1:1 ?
[Edited on 24-12-2011 by allchemy]
Attachment: A puzzle from the Mitsunobu reaction.doc (21kB)
This file has been downloaded 915 times
[Edited on 25-12-2011 by allchemy]
[Edited on 25-12-2011 by allchemy]
[Edited on 25-12-2011 by allchemy]
|
|
|
Dr.Bob
International Hazard
Posts: 2736
Registered: 26-1-2011
Location: USA - NC
Member Is Offline
Mood: No Mood
|
|
Perhaps your triphenylphosphine is already partly oxidized at the start. We found that older bottles tend to have some oxidation occur just from
air. I don't remember the exact details, but that can cause both poor yields, and harder workups.
We also tried the pyridine version of the Ph3P, which is supposed to extract into acid, but we had poor luck getting that to work. What we did have
some luck with was using triphenylphosphine bound to resin, but that cost is very high unless you can recycle the resin back and reuse it. And of
course the DIAD goes bad fast also if not stored cold enough. They are great reactions for small scale, but very hard to scale up without a large
cost and purification battle.
|
|
|
allchemy
Harmless
Posts: 4
Registered: 23-12-2011
Member Is Offline
Mood: No Mood
|
|
Revise my writing error
Triphenylphosphine(not phenol,I have got it wrong ) and DIAD mole ratio is about 1:1. In the termination,the total triphenylphosphine oxide and
diisopropyl hydrazodicarboxylate should also approach 1:1,however, the total triphenylphosphine oxide is far outweigh diisopropyl
hydrazodicarboxylate. I'm puzzled.
My product is belong to fine chemicals,easy to purificate.
DIAD goes bad fast if not stored cold enough,is it true?]
[Edited on 25-12-2011 by allchemy]
|
|
|
allchemy
Harmless
Posts: 4
Registered: 23-12-2011
Member Is Offline
Mood: No Mood
|
|
The manufacturer said that the DIAD purity is >98%
|
|
|
ThatchemistKid
Hazard to Others
Posts: 132
Registered: 2-6-2010
Member Is Offline
|
|
Are you sure the DIAD is not a solution of 40% concentration in toluene...generally from what I have seen that is how DEAD is sold. DIAD maybe the
same. Also DIAD does decompose if not stored in a fridge though not as fast as DEAD.
|
|
|
Dr.Bob
International Hazard
Posts: 2736
Registered: 26-1-2011
Location: USA - NC
Member Is Offline
Mood: No Mood
|
|
It was that pure (maybe, they tend to exaggerate purity IMO) when it was manufactured. From that date on, the purity will go down, faster if not
stored cold.
The same goes for the triphenylphosphine, it will start oxidizing from the moment it is manufactured unless kept away from oxygen, and most plastic
bottles don't keep out oxygen well. Even glass ones will let it in when opened. So its purity will drop over time.
Some chemicals, like benzoic acid, phenol, most salts, and non redux active chemicals will stay pure upon storage. Most amines, phosphines, azo
compounds, aldehydes, and other reactives will degrade in storage, some alarmingly fast. I was surprised to learn how fast fluorobenzylamines (I
don't remember which isomers we checked) would degrade, even in new, "sealed", bottles, when we tested them by GC-MS over a few weeks. They had air
oxidized to the imine, which then reacted with the amine to form new products, which then formed new peaks. Within a month, the material had gone
from about 96% pure (label said 99%) to under 70% pure, with a number of secondary amines, carbonates (from absorbing CO2 in air), imines, and complex
crap in it.
So don't think the purity on the label is good forever. It might not even be right with a new bottle.
|
|
|
![[*]](images/xpblue/default_icon.gif){kind=icon}
