Sciencemadness Discussion Board

Carbolithiation of N-alkenyl ureas to a hindered amine?

Hockeydemon - 30-7-2013 at 04:51

This is probably outside of my capabilities, but I figured I'd ask about the possibility of it.

I was thinking I could perform a SN2 reaction with
1-butanol + HCl --> chlorobutane

Then react chlorobutane with lithium to form the super base n-Butyllithium

Then synthesize a alkenylcarboxlate (haven't decided on a route)

Then react the alkenylcarboxlate with urea to form n-alkenyl urea

Then a carbolithiation of N-alkenyl urea with the n-butyllithium which results in a hindered amine.

I'm not really sure what I would use a hindered amine for, but I stumbled across these while looking for various reactions to perform.


[Edited on 30-7-2013 by Hockeydemon]

bbartlog - 30-7-2013 at 11:52


See whether you can do the first step. Seems to me like it would be dog slow without ZnCl<sub>2</sub> catalysis. Or you could use HBr and end up with 1-bromobutane instead - that prep is described in 'Experiments in Organic Chemistry', in the forum library. No catalyst needed for that one.

Hockeydemon - 30-7-2013 at 13:37

Quote: Originally posted by bbartlog  

See whether you can do the first step. Seems to me like it would be dog slow without ZnCl<sub>2</sub> catalysis. Or you could use HBr and end up with 1-bromobutane instead - that prep is described in 'Experiments in Organic Chemistry', in the forum library. No catalyst needed for that one.


I went ahead and added 2mL HCl & 2mL 1-butanol to 3mL H2O with a dash of NaCl. I then proceeded to heat that with a bunsen burner. There are now two immiscible layers in the test tube, the top layer is a incredibly light tan/slightly cloudy (would be clear without the contrasting lower layer) while the bottom layer is slightly cloudy, but more clear than the top layer.

I'm not sure how to test to see if I made chlorobutane, but I'll start googling I guess.

bbartlog - 30-7-2013 at 14:57

Sounds like you salted out your butanol from the aqueous, briny part of your HCl. The layers are not evidence for a reaction, in other words.
I don't know of a qualitative test for chlorobutanol but if I were to attempt this I would want reflux gear, and large enough reagent volumes that I could take a boiling point on the vapors as they distilled over.