BIOTECHNOLOGY LETTERS

Volume 15 No.12 (Dec.1993) pp.l243-1244

Received 4th November

LIPASE CATALYSED ESTERIFICATION OF ISOSORBIDE AND SORBITOL

D.Mukesh*, D.Sheth, A.Mokashi, J.WagQ,

J.M.Tilak, A.A.Banerji, K.R.Thakkar

Alchemie Research Centre, P 0 Box 155, Thane-Belapur Road,

Thane-400601, Maharashtra, INDIA.

Supported lipozyme catalysed esterification of isosorbide and

sorbitol individually with oleic acid is studied in a tubular
recycle reactor which is packed with enzyme, silica gel and solid
reactant. Isosorbide produces only monooleate while sorbitoi
produces both mono and dioleates during the reaction.

INTRODUCTION

Fatty acid esters of anhydrosorbitols are the second largest

class of carboxylic ester surfactants. They find application in
food, detergent and cosmetic industries. Anhydrosorbitol esters
are prepared commercially by direct esterification of sorbitol
with a fatty acid at 225-25O'C in the presence of an acid
catalyst. During this reaction dehydration occurs to varying
degree, giving rise to a mixture of mono and di esters of
sorbitol, sorbitan and isosorbide (Kirk and Othmer, 1990). Hence
the commercial ester is a mixture. Therefore there is some need
for developing a process for the preparation of a single ester
of anhydrosorbitol. Enzyme catalysed esterification of D-sorbitol
and decanoic acid is reported by Janssen etal. (1990), while
esterification of carbohydrates in a wide range of solvents is
reported by Riva et al. (1988).

In this paper immobilized lipase catalysed esterification of

isosorbide and sorbitol individually with oleic acid is described

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 without any solvent. The reaction is carried out in a tubular
reactor packed with the enzyme, solid reactant and silica gel.

MATERIALS AND METHODS

The tubular reactor consisted of a jacketed glass tube 19 cm long
and 2.13 cm in diameter provided with a thermowell and a heating
tape. 7 g of immobilised lipase (Lipozyme, IM-20,Nova-Nordisk,
Denmark, average particle size 0.25 - 0.65 mm) was mixed with 15
g of silica gel and 1O'g of isosorbide or sorbitol (Aldrich) and
packed into the tube to achieve a voidage of 0.40. 60 cc of oleic
acid was pumped from one end of the reactor. The product mixture
was collected and pumped back again to achieve recycle action.
The pumping rate was adjusted to achieve a flowrate of 3 cc/min.
Experiments with sorbitol were also carried out with 0.1 g of
sorbitan monooleate, a surfactant added to the oleic acid, to
achieve better solid-liquid contact.
Samples were withdrawn at definite time intervals and their acid
value determined (Mukesh etal., 1993). The product was analysed
by GPC (p-Styragel 500,500,100,100 AD columns, provided with a
R.I. detector. The solvent was THF at a flow rate of 1.5 cc/min
and a pressure of 1000 psi.). The isosorbide based product was
also analysed by HPLC (l-fatty acid analysis column equipped with
a variable length W detector at 204 nm). The initial solvent
mixture of CH,CN/H,O (at 5/95) was linearly varied to pure CH,CN
over a period of 20 mins. The flow rate of the solvent mixture
was maintained at 1 cc/min.
RESULTS AND DISCUSSIONS

Figure 1 shows the isosorbide and sorbitol conversions as a

function of time at different operating conditions. Although both
isosorbide and sorbitol are solids, as they are sparingly soluble
in oleic acid, the esterification reaction proceeds reasonably
well.' The product ester is completely sol&e in oleic acid. The
conversion is highest with isosorbide (95 % in 13 hrs), when
compared to sorbitol. Addition of a surfactant sorbitan
monooleate to oleic acid improves the esterification reaction
with sorbitol (see curves 2 and 3 in figure l), by improving the
contact between the solid and liquid reactants.

The esterification reaction produces only endo (internal) and exo

(external) monooleates of isosorbide, the former being three
times more than the latter. It is reported (Buck et al, 1963)

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 Figure 1 Esterification
kinetics-60 cc oleic
acid, recycle rate=3
cc/min, 50C.(1-iso-
sorbide, 2&3-sorbitol;
without and with sorbi-
tan monooleate).

that the endo hydroxyl of isosorbide, which is involved in intra

molecular hydrogen bond formation, is more easily esterified,
than the exo hydroxyl. No dioleates are found in the product. On
the contrary, sorbitol produces both mono and dioleates (see
figure 2). The mono oleate fraction decreases and the dioleate
fraction increases with time, indicating formation of the former
first followed by the latter as expected. The terminal hydroxyls
of the sorbitol are the ones probably taking part in the
esterification reaction. It is reported that the secondary
hydroxyls of sorbitol esterifies at a much slower rate than the
primary hydroxyls (Bailey, 1964).

CONCLUSIONS
Enzyme catalysed esterification of isosorbide and sorbitol with
oleic acid is described here. The reactants are sparingly soluble
in oleic acid, but as the reaction proceeds ester is formed,
which being a surfactant probably hastens their dissolution in
the acid. Also, the water formed during the reaction is removed
insitu, which drives the reaction forward. The rate of

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 Figure 2 Product
distribution-sorbitol
esterification.(l-mono
& 2-dioleate. See fig.1
for conditions).

esterification reaction is higher with isosorbide than with

sorbitol. Addition of sorbitan monooleate improves the rate of
reaction in the case of sorbitol.

ACKNOWLEDGEMENTS
The authors thank ICI India Ltd. for financial support.

REFERENCES

Bailey, A. E. (1964), In industrial oil and fat products, Ed.

Swern, D., 3rd edn., Interscience, Chichester.
Buck, K. W., Foster, A. B., Perry, A. R., Webber, J. M. (1963),
J. Chem. Sot., 4171-4177.
Janssen, A. E. M., Lefferts, A. G., van't Riet, K. (1990) I
Biotech. Letters l2, 711-716.
Kirk and Othmer (1981), Encyclopedia of Chemical Technology, 3rd
edn., Wiley-Inter Science Publn., John Wiley & Sons, New York.
Riva, S., Chopineau, J., Kieboom, A. P. G., Klibanov, A. M.
(19881, J. Am. Chem. Sot. 110, 584-589.
Mukesh, D., Jadhav, S., Sheth, D., Banerji, A. A., Newadkar, R.,
Bevinakatti, H. S. (1993), Biotech. Techn. 1, 569-572.

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