BuLi Titration
BuLi Titration
BuLi Titration
1) The GILMAN Double Titration (J. Organomet. Chem. 1964, 2, 447 – 454.)
The most reliable method to determine the concentration of an organolithium is still
the double titration procedure described by Gilman 40 years ago. It is preferred over
single titration methods because it not only gives the concentration of the solution but
also provides an indication of the quality of the organolithium.
To determine the total content of base, an aliquot (usually 0.50 to 1.5 ml, depending
on the expected concentration) of the solution of the organolithium is quenched with
20 ml of water. The resulting solution of LiOH is titrated with a solution of
standardised hydrochloric acid using phenolphthalein as the indicator. To determine
the residual content of base of the organolithium, an aliquot (preferably the same
amount as before) of the organolithium is reacted with 1,2-dibromoethane as follows:
0.20 ml of dry 1,2-dibromoethane (BE CAREFUL: CARCENOGENIC) are dissolved
in 3 ml of dry DEE in an inert atmosphere. The organolithium is added dropwise with
vigorous stirring. After 5 min of stirring, the solution is diliuted with 20 ml of water
and then titrated as described above. 1,2-Dibromethane reacts with organolithiums as
follows:
R Li Br R H LiBr
Br Br
This procedure destroys the organolithium without producing LiOH, so that the
difference of the two titrations gives the exact concentration of the organolithium. A
typicale example is given below:
I. A 0.50 ml aliquot of a solution of n-BuLi in hexanes was quenched with water,
treated with a few drops of a phenolphthalein solution in water/methanol and titrated
with standardised hydrochloric acid unitil complete disappereance of the pink colour.
When titrating highly flammable organometallics such as t-BuLi, step I should be
carried out with degassed water under nitrogen.
II. A second 0.50 ml aliquot was quenchend with dibromoethane as described above.
After 5 min of stirring, the mixture was diluted with water and after addition of the
indicater titrated (with vigorous stirring – it is a biphasic system).
c(HCl) = 0.1034 N; V(HCl)I = 7.90 ml; V(HCl)II = 0.25 ml.
V(HCl)eff = V(HCl)I – V(HCl)II = 7.90 ml – 0.25 ml = 7.65 ml
c(n-BuLi) = [V(HCl)eff x c(HCl)] / V(aliquot) = [7.65 ml x 0.1034 mmol ml-1] / 0.50 ml
= 1.58 M
Residual base = [0.25 ml / 7.90 ml] x 100 % = 3.2 %. This value is typical for a high
quality organolithium. If the content of residual base is higher than ~ 10 % of the total
content of base, the quality of the organolithium is poor, which may be detrimental to
very sensitive reactions.
H Li
Ts BuLi Ts
N N
N H N Li
red-orange
For a discussion of other titration methods see: J. Suffert, J. Org. Chem. 1989, 54,
509.