Separation of a mixture of n-butyl acetate and n-butanol

using a deep-eutectic solvent (DES)

Reagents:
n-butyl acetate& n-butanol mixture, Choline chloride & Glycerol mixture (or deep-eutectic
solvent, DES)

(2-Hydroxyethyl)trimethylammonium chloride

Glycerol

Note: Ethylene glycol can be used instead of glycerol!

Prepration of Choline chloride (incase unavailable!)

Choline chloride (ChCl) can be prepared from, trimethylamine (TMA), HCl and Ethylene oxide
(EO) as shown in the reaction schemes below. Reactions are fast and exothermic!

[H(CH3)3N+]Cl-

HCl + (CH3)3N

trimethylamine hydrochloride
(TMA-HCl)

[H(CH3)3N+]Cl-

N+
OH

Ethylene oxide

Cl-

Choline Chloride, ChCl

Apparatus/equipment
Glass ware: separating funnels, beakers, measuring cylinders etc; Shaking apparatus;
Centrifuge; Gas chromatograph

Experimental Procedure

1. Put a known volume (e.g. 50 ml) of ester/alcohol mixture (at ambient conditions) into a
separating funnel.
2. Add a deep-eutectic solvent (DES) into the ester/alcohol mixture in a volume ratio of 5:1
(DES: Ester-alcohol solution) respectively.
3. Mix or shake the solution mixture in the separating funnel vigorously for at least 5 min.
4. Stop shaking and let phases in funnel separate
5. Decant off the bottom (heavy) phase (butanol loaded DES solution) and keep aside!
6. Take a sample from the upper (light) phase (butanol raffinate), centrifuge and recover a
clear organic sample for GC analysis
7. Contact the upper phase (in step 5-6 above) with fresh DES solution in the same
volumetric ratio as in step 2. Repeat steps 3-6!
8. Repeat step 7 three times, i.e contact the ester/alcohol mixture in step 1 at least a total
of four times with fresh DES solution in each contact.
9. Remember to record the actual volumes of solutions used in each contact!
10. Keep the bottom phase in each case for further tests (stripping of n-butanol with water
from DES maybe necessary!)
11. Gas chromatographic (GC) analysis: analyze the raffinate solutions to determine the
purity of butyl acetate.

Figure 1. Illustration of Liquid-liquid separation of ester/alcohol mixture using DES reagents. [1]

References

1.

Zaira Maugeri, Walter Leitner & Pablo Domnguez de Mara (2012) Practical separation of alcoholester
mixtures using Deep-Eutectic-Solvents, Tetrahedron Letters 53, pp.69686971

2.

Scott Handy & Kevin Lavender (2013) Organic synthesis in deep eutectic solvents: PaalKnorr reactions,
Tetrahedron Letters 54, pp.43774379

3.

Choline chloride, [online],

available:http://www.sigmaaldrich.com/MSDS/MSDS/DisplayMSDSPage.do?country=FI&language=ENgeneric&productNumber=C7017&brand=SIGMA&PageToGoToURL=http%3A%2F%2Fwww.sigmaaldrich.co
m%2Fcatalog%2Fproduct%2Fsigma%2Fc7017%3Flang%3Dfi [November 8th, 2015]

4.

Glycerol, [online], available:

http://www.sigmaaldrich.com/MSDS/MSDS/DisplayMSDSPage.do?country=FI&language=ENgeneric&productNumber=G5516&brand=SIGMA&PageToGoToURL=http%3A%2F%2Fwww.sigmaaldrich.co
m%2Fcatalog%2Fproduct%2Fsigma%2Fg5516%3Flang%3Dfi [November 8th, 2015].

5.

Johnson Matthey Davy Technologies Limited, [online], available: http://davyprotech.com/what-wedo/licensed-processes-and-core-technologies/licensed-processes/choline-chloride/specification/ [November

8th, 2015]