[Kaladiscope]

Hi,

I am aware that amine and alcohols react with PCl3 to form aminophosphines and phosphites respectively.

I am wondering what should be more reactive towards PCl3 having in the same molecule an alcohol and an amine.

Since is just a substitution reaction, I guess that the more nucleophilic atom (nitrogen in this case) will react faster with the Phosphorous generating first the corresponding aminophosphine...

What do u think...

[discodermolide]

You mean something like ethanolamine? Probably the amine will attack first removing a Cl- which will form HCl and hence the HCl/amine salt of another ethanolamine. Then the reactivity of the amine will decrease and the alcohol will attack thereafter.

[Kaladiscope]

Or something like 4-aminophenol.

I agree with your suggestion...but I was just thinking what should happen if we add here any base, like NEt3.

As before NH- will attack first, forming Cl2PNHPhOH. But here the difference from my point of view is that we will generate a HNEt3, which will keep intact the reactivity of another the aminophenol itself generating an another subsitution, Cl(PNHPhOH)2, and finally again to form finally P-(NHPhOH)3. Since deprotonation of amine proton is more favoured than phenol alcohol I don't think that the alcohol will interfere or react at all with Phosphorous...

[discodermolide]

I think you are correct in your assessment. Adding a base will permit the desired amine to react, as you describe.