THE PREPARATION OF SUCROSE MONOESTERS*

R. U. L E M I E U X ~ 4 . G. MCINNESS
AND
Department of Cheiizistry, University of Otta~oa,Ottawa, Ontario
Received July 16, 1962

ABSTRACT
The Snell procedure for the preparation of sucrose monoesters of the higher saturated
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fattp acids by transesterilication of sucrose and rnethyl esters in N,N-dirnethylfor~~ia~~iide

was found to yield variable results due to the use of solid potassium carbonate as catalyst
and to inlpurities in the solvent. A kinetic study of the reaction revealed t h a t yields of sucrose
ester and rates of reaction were reproducible when conditions for homogeneous catalysis were
established. The reaction followecl first-ordcr kinetics in methyl ester and s ~ ~ c r a tion e and
the rate of reaction was essentially independent of the sucrose concentration, the molecular
weight of the fattp acid, and the nature of the metal sucrate used to catalyze the reaction.
The activation energy for the reaction \x7as 0.0 Ixal n~ole-I. E q ~ ~ i l i b r i u mconstants for the
principal reactions were determined, and it was established that only the thermodynamic
t transesterilication reaction. A preparative
product prevailed a t any t i ~ n et h r o ~ ~ g l l o uthe
method for the synthesis of sucrose monoesters was developed that gave yields of sucrose
ester, based on the amount of methyl estcr which had reacted, which were essentially quanti-
tative. The product contained a l ~ o u t20'7; of di- and 80% of mono-ester.

In 1'354 Snell and co-workers developecl a process for the preparation of fatty acid
Can. J. Chem. 1962.40:2376-2393.

esters of sucrose ( I ) using the transesterificatioi~ reaction, which was subsequently

published in 195G (2). T h e procedure was based on the reaction of sucrose with the
methyl ester of a fatty acid, in N,N-dimethylfoi-~namide( D M F ) solution, using solid
potassium carbonate as a catalyst. T h e methanol formed in the reaction was removed
i 7 z vaclro uitder co~lditionsfor fractioilal distillation. This process attracted considerable
interest from industry a s a means for the preparation of sucrose monoesters of the higher
fatty acids for use as low-cost, 11011-ionic cletergents (3, 4).
T h e elucidation of the structures of the sucrose monoesters formed and the deter-
m i ~ l a t i o iof~ their relative amounts in the products obtained first attracted our attention
t o this process. I-Iowever, when an attempt was made to prepare samples of sucrose
mo~loester,by the original Snell proceclure (2), for structural analysis, it soon became
apparent that the product clid riot warrant such an investigation since it coulcl not be
prepared uncler fully controlled ancl reproducible conditions. For un1;nown reasons,
l ~ i g l ~ variable
ly yields mere obtained and the products differed considerably in the degree
of substitution, solubility, and color even when the reaction was performecl under apparent-
ly iclentical experimental conclitions ( 5 ) . Although other workers have claimed more
success in this respect a critical assessment of their results clearly inclicates t h a t they
have been equally unsuccessful i l l preparing reproducibly a product in high yield (2,
6-8). Furthermore, the concl~~sions which the various workers have drawn (2, 6-11) from
their experimental results are often in conflict, and in direct opposition to m o d e r ~con- ~
cepts on the mechanism of trallsesterificatio~ireactions. Snell and co-wor1;ci-s, for example,
have claimed t h a t stlcrose monoester was esterified so inuch faster than sucrose that
higher-substitutecl esters of stlcrose accumulated in the first stage of the reaction and
subsequently reacted with the excess sucrose to re-form sucrose monoesters (2). They
also concluded t h a t the concentration of sucrose monoester in the final product was
* T h i s p(~perW(LS siibilvitled by A . G. :lf~.Iizne.r(IS n orti ti on of n thesis for the I'1i.D. degripe.
tl'reseizt czddress: Dejmrtnient of Clieii~istry,University of Alberta, E d n ~ o n t o ~Alberta.
z,
$I'resewt c~ddress:iltlaiztic Regional Laboratory, iV(~tioncz1Reseniclz Coziizcil, fIal$(~.t., 9 o r a Srotia.
Canadian Journal of Chemistry. T'olume -10 (19G2)

2376
 LEMIEUX AND MCINNES: SUCKOSE MONOESTERS 2377

dependent on the amount of s o l v e ~ ~ (DRJF)

t in which the reaction was carried out (2),
and on the concentration of water in the reaction solution (6). i\Joreover, their results
indicated that the only effect of increasing the catalyst co~~centration was to increase
the soap content in the product of reaction (2). Worlters a t the Herstein Laboratories
(7, 8 ) , on the other hand, have claimed that the sucrose monoester content was dependent
on the catalyst concentration and was independent of the moisture content in the
reaction solution. The latter worlters also claimed that the cation of the catalyst chelates
with the sucrose molecule, and that it was this chelate complex which was the effective
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catalyst in the reaction. They concluded that different cations produced a product with
different sucrose mono- to di-ester ratio, and have suggested that this is in some xiray
related to the ionic radius of the cation (7). For example, it was claimed that lithium
produced only sucrose monoester whereas potassium produced sucrose diester also. This
specificity was attributed to the fact that lithium, which has a smaller ionic radius
than potassium, cannot form a chelate with two hydroxyl groups a t the same time, in
contrast to potassiu~ll (7). Furthermore, the sucrose diester concentration was found
to increase with increasing cation-sucrose co~llplexconcentratio11 (7, 8), a t least for those
catalysts with the necessary ionic radius. Herstein and his co-workers have also claimed
that an equilibrium exists between sucrose, sucrose diester, and sucrose monoester in
the reaction solution (7). 111 spite of this observation, however, they evaluated the
Can. J. Chem. 1962.40:2376-2393.

opti~llalconditions for the transesterifcation reaction by orthogonal statistical design

(7, 8), and reached the co~lclusio~l that although an equilibrium existed betxireen sucrose,
sucrose diester, and sucrose monoester, the concentration of the latter passed through
a m a x i m ~ ~ with
m increasing sucrose concentration and then decreased with a further
increase in the sucrose conce~~tration. I<omori and co-worlters (9, 11) have reported that
the rate of trai~sesterificationwas dependent on the sucrose concentration.
In contrast to the above concl~~sions, mechanistic studies have established that trans-
esterifications are reversible reactions (12) which exhibit first-order kinetics in ester and
alkoxicle ion (13). In view of the apparent co~ltradictio~ls and the important role the
conditions for tra~lsesterificatio~lby the Snell procedure promise to have in carbohydrate
'chemistry, it was decided to co~lducta careful kinetic study of the reaction and t o
determine the equilibrium constants for the principal reactions.

ESPERIMEN'I'AL A X D RESCLTS
Materials
In all experiments the D M F was distilled from phosphorus pentoxide, and only the fraction boiling
a t 153-154" a t atmospheric pressure was used. 'The sucrose, [ a ] fGG.50
~ (c, 22; water), was storecl over
phosphorus pentoxide under reduced pressure. T h e methanol was driecl by distillation from magnesiui~~
methoxide. The methyl myristate, methyl palmitate, and 71-octadecane each had a purity greater than
99.5 mole% when analyzed by gas-liquid partition chromatography (GLPC). T h e illethyl stearate con-
tained 9.0 mole% of niethyl myristate, methyl palmitate, and a n unidentified ester having a retention
volume corresponding to t h a t expected for a C ~ fatty
T acid methyl ester. Since these methyl esters con-
tained no free fatty acid they were used without further purification. 71-Octadecane \\.as soluble to t h e
extent of 4.5 g/300 ml of reaction solution a t SOo. All other solvents were reagent grade.
Methyl myristate was ~isecl in all reactions unless otherxvise specified.
Rate 116easzrre1nenls
All rates of reaction were determined b y following the decrease in concentration of the methyl ester
of a fatty acid b y GLPC (14) using 71-octadecane a s a n internal standard. T h e apparatus used for the
analyses was a "Pye Argon Chronlatograph", and some of the pertinent characteristics are listed below:
Column size, 4 ft, 5-mm I.D. Resol~ition,lip to 1000 theoretical plates/ft
Detector, ionization (80 pc r a d i ~ u uD) Limit of detection, 0.01 y
Carrier gas, argon Colu~nnpaclting, Ceiite 545:Apiezon 17 ( 9 3 , w/w)
Saniple size, 3-6 y Column temperature, 200' C
 2378 CANADIAN JOURNAL OF CI-IBMISTRY. VOL. 40, 1962

T h e calibration of apparatus is shown in Fig. 1 and the retention vol~rmesa t 200° of the methyl esters
of myistic, palmitic, and stearic acids, relative to t h a t (1.0) of n-octadecane, were 0.57, 1.38, and 3.22,
respectively.
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MOLAR RATIO

FIG. 1. T h e plot of the ratio of the areas obtained for standard mixtures of methyl.myristate and
n-octadecane when analyzed by gas-liq~~idpartition chromatography against the lcnown molar ratio.
Can. J. Chem. 1962.40:2376-2393.

Standard Transesterification Reaction Conditions

The transesterification apparatus is shown in Fig. 2.

FISHER HITEMP BhTH t 4 . l l t E T O N E TRIIP,.,9.,

C0.-KETONE T R I P (-19.1

FIG. 2. T h e transesterification apparatus.

An attempt was made to remove the last traces of water from the reaction s o l u t i o ~by~ conditioning
the reactants in the following manner. Sucrose, 60 mmole, was dissolved in 300 n ~ of l anhydrous D M F
and conditioned a t 80f 0.5" a t 75 inn1 pressure for 30 minutes. The oil-bath temperature was 8 9 f l o , and
the reaction solution was stirred mechanically and had a fine stream of dry nitrogen passing through it.
A 50-ml volume of petroleun~ether containing 20 mmole of methyl ester and 12.75 nlmole of n-octadecane
was then added to the D M F solution, and the petroleum ether was removed rapidly under reduced pres-
sure. After 30 minutes the reaction solution temperature was again constant a t 80" a t 75 nun pressure. A
 L E M I E U X AND McINNES: SUCROSE MONOESTERS 2379
0.6-ml aliquot of the D M F sol~itionwas then talcen and analyzed by G L P C (see below). T h e catalyst
was then added to the reaction solution a s a solid or a s a methanolic solution a t atmospheric or 75 m m
pressure, respectively. In the former case a reaction temperature of 80" a t 75 rnln pressure was established
a s quiclcly as possible, and in the latter case the catalyst solution was injected into the reaction solution
with a hypodermic syringe through the silicone rubber seal on the reaction vessel (see Fig. 2) while the
apparatils was ~ ~ n c l reduced
er pressure. During the course of the transesterification reaction the temperature
a t the top of the Vigreaux colum11 remained constant a t 2 9 f lo.T h e reaction solution had a total volume
of 320 ml.
T h e progress of the reaction was followed b y withdrawing a t intervals of time 0.6-ml aliqi~otsof the
reaction solution, by means of a hypodermic syringe fitted with a 3-inch needle, through the silicone rubber
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seal (see Fig. 2) without disturbing the vacuum in the apparatus. These solutions were diluted with 0.6 ml
of a 5% sodium chloride solution and the methyl ester and n-octadecane were extracted with 0.5-1111 amounts
of a 3:l petroleum ether/ether solution. A 0.1-pI aliquot of the latter was then analyzed by GLPC. When
standard mixtures of methyl rnyristate and n-octadecane in a 0.2 dC solution of sucrose in D M F were
analyzed in this manner the results were identical with those obtained using petroleum ether solutions
of the co~npoilndsfor calibration (see Fig. 1).
T h e yields of sucrose ester a t the end of the reaction period were obtained, in duplicate, on 25-1111 aliquots
of the reaction mixture. Each aliquot was first cooled to 20' by the addition of solid carbon dioxide, and
the n-octadecane and unreacted methyl ester were removed quantitatively b y extracting the D M F solution
with three 50-1111 aliquots of petroleum ether. The D M F solution was then taken to dryness a t 70' under
reduced pressure and the residue was dissolved in 25 ~ n of l 71-butanol. The latter was washed with two
25-ml volumes of 5% sodium chloride solution to remove the catalyst (in the form of a metal carbonate)
and unreacted sucrose, and the combined aqueous phase was re-extracted with 15 ml of n-butanol. Ally
sodium chloride in the combined n-butarlol phase was precipitated by the addition of 40 rnl of chloro-
form. After drying of the chloroform/n-butanol solution with 10 g of anhydrous sodium sulphate overnight
Can. J. Chem. 1962.40:2376-2393.

the salts were removed by filtration, the latter being washed with a further 40 1111chloroform. The filtrate
was talcen to dryness under reduced pressure. Ethanol was then added and the mixture was evaporated
in order to remove the last traces of 71-butanol and D M F . The white residue of sucrose ester was dried
under reduced pressure over phosphorus pentoxide.
T h e percentage yields of sucrose ester were based on the complete conversion of 20 mmole of methyl
ester to sucrose mono~nyristate(denoted P ) or on the amount of methyl myristate which had reacted
(denoted P I ) .

Routine Tests for the Presence of Ifnpurities in the Szicrose Ester

T h e sucrose ester, 50 mg, was dissolved in 1 rnl chloroform a t room temperature. In the absence of sucrose
and sodium chloride a clear solution free of insoluble residue was obtained. A 0.1-pI aliquot of the above
chloroform solution was analyzed by GLPC for methyl ester and n-octadecane. An infrared spectrum
of the above chloroform solution was taken. T h e presence of D M F or the anion of a fatty acid could be
detected since they have characteristic absorptions, for the C=O stretching vibration, a t approximately
1680 and 1560 cin-I, respectively. An aqueous solution of the sucrose ester was also tested for chloride
ion with silver nitrate.
All the samples of sucrose ester prepared using the above standard procedure gave negative results
for these tests.

The Tmnsesterijication Reaction Using Solid Potassiunt Carbonate

The standard transesterification reaction conditions were used, and 4 meq of solid potassium carbonate
were added to catalyze the reaction. Furthermore, the reaction was carried out (a) without mechanical
stirring or nitrogen passing through the solution, (b) without mechanical stirring and with nitrogen passing
through the solution, (c) with nlechanical stirring and nitrogen passing through the solution, and (d) with
the same reaction conditions as (c) except that the potassium carbonate had been impregnated on 1 g of
Celite by admixing a 1-ml aliquot of a n aqueous solution of potassium carbonate with 1 g of acid-washed
Celite and drying the mixture a t 180' for 48 hours before use.
Results for single experiments satisfying the above experimental conditions are given in Fig. 3. Reaction
solutions (a), (b), (c), and (d) gave values of 41.2, 70.7, 87.8, a n d 79% for P after 7, 24, 7, and 4 hours,
respectively. T h e corresponding values for PI were 71.1, 70.5, 87.8, and 82.8%. Considerable variations
in the rates of reaction and yields of sucrose ester were obtained when attempts were made to reproduce
these results in duplicate experiments. Moreover, it was observed that all the solid potassium carbonate
did not dissolve in any of the experiments. I t was apparent that variable amounts went illto solution.

The Effect of Water on the Transesterijication Reaction at 80' using Solid Potassiunz Carbonate a s Catalyst
T h e reaction conditions in (c) above were used.
T h e initial concentration of water in the reaction solutions were 0.01, 0.05, 0.25, and 1.2570, which
corresponded to the addition of 0.42, 2.10, 10.5, and 52.5 inmole of water per meq of solid potassium
carbonate. The water was added to the reaction solution after the usual 1-hour conditioning period, and
 2380 CANADIAN JOURNAL O F CIIHMISTRY. VOL. 40, 1962
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Time in H o u r s Time in H o u r s

FIG. 3 . Rates of transesterific:~tion a t 80' using -4 meq of solicl p o t a s s i ~ ~ carbonate

m as tlie catalyst. T h e
reaction solutions were stirred mechanically in ( r ) and ( d ) . X stream of nitrogen was passecl through tlie
solution in ( h ) , ( r ) , and ( d ) . 'She catalyst in (d) was impregnated on Celite.
FIG. 4. 'l'lie effect of adding 1.68, 8.4, 42, and 210 rnmole of water on the rate of transesterilication
a t SOo, using 4 nleq of solid potassium carbonate as thc catalyst. 'The reaction solutions were stirred mechan-
ically, ant1 scrubbed with a stream of nitrogen.

a t the same time as the catalyst. T h e p o t a s s i ~ ~carbonate

~n did not dissolve co~iipIetelyin any of these
experiments.
T h e effect of water on the rate of reaction is shown in Fig. 4. Yields of sucrose myristate of 82.2, 81.5,
Can. J. Chem. 1962.40:2376-2393.

31.0, and 32.3% for P , and 93.8, 87.7, 66.5, and 93.5% for P I were obtained for the experiments containing
0.42, 2.10, 10.5, and 52.5 mmole of water, respectively.
Tial~sc~steri$catioltReactions u s i n g Sodizlm H y d r i d e a n d Satl~ratedSolulr'ons of Potassizrnl Ca~boltate
T h e transesterification reaction was carried out in the ~ ~ s u manner al using D M F or D M F plus sucrose
solutions saturated with p o t a s s i ~ ~ carbo~late.
m These solutions were prepared by heating 300 ml of D M F ,
or 300 ml of DMF containing 60 mti1ole of sucrose, with 4 meq of solid potassium carbonate a t 80" for
18 and 6 hours, respectively. After relnoval of a n y solid material, by filtration, under anhydrous conditions,
the filtrate was used for the transesterification reaction. Titration of aliquots of the D M F solution con-
taining only potassium carbonate revealed that it was 0.0014 M in potassium ion. The latter solution gave
only 9.97; reaction in 4 hot~rs,and gave sucrose myristate values of 9.5 and 96.2Yh for P and P I , rcspec-
tively. T h e D M F plus sucrose solution of potassil~rncarbonate, on the other hand, gave 56.0% reaction
in 6 hours, and gave yields of sucrose ~nyristateof 48.4 and 86.3% for P and P I , respectively.
Another transesterification reaction carrictl out using 300 rnl D M F , 60 mmole sucrose, 20 mmole methyl
myristate, and 4 meq sodium liydride a t SO0, a t 190 mm pressure, on a rotary evaporator, gave 52y0
reaction in 6 hours, and sucrose myristate yields of 40.8 ancl 78.5% for P ancl P I , respectively.
T h e Transesteri$catio~t Renc-liolz zlltder Conditiolzs for Hon7ogeneoz~sCnttrlysis
The yields of sucrose myristate as \\,ell a s the ratcs of reaction are given in Table 1.
All of the reactions reported in Table I were carried out in homogeneous solution a t 80' under identical
conditions of pressure and mechanical stirring, and with nitrogen bubbling through the reaction solution.
In order to obtain homogeneous reaction conditions the catalyst (4 meq) was added to the reaction solution
as a dilute solution in 5 rnl anhydrous methanol or a s a sat~lratetlmethanolic or aqueous solution. Potassium
carbonate, potassium methoxide, litlii~umniethoxide, sodium metlioxicle, and potassium hydroxide were
all used to catalyze the reaction.
T h e Effect of SSSSSSSS?~~~.~~~
Collcelttraticlz o n the R a t e of Reactiolz nt SO0
The rates for the standard transesterification reaction together with the yieltls of sucrose ~ilpristateare
given for three concentratio~isof sucrose, namely 60, 40, and 20 mmole, respectively, i l l 'Table 11. A saturated
methanolic solution of potassi~~ln niethoxitle containing 4 mcq of the latter in 0.68 mi solution was used
as catalyst.
T h e Effect of Fatty A c i d Cltwin Lelzgth 011 the R a t e of Reaction a t SOo
P o t a s s i ~ ~methoxide,
m 4 meq, in 5 ml anhydrous methanol was used to catalyze the reactions. T h e data
for the three methyl esters are give11 in Table 111. T h e pseudo first-order rate constants for the standard
transesterification reaction using methyl myristate, methyl palmitate, and methyl stearate were found
t o be 3.33, 3.17, and 2.06X10-.'~ec-~, respectively.
T h e Effect of Goseoz~sC a ~ b o l zDioxide 011 t11e R a t e of T r a ~ ~ s e s t e r i $ c a t i at
o ~SOo
The standard transesterilication reaction conditions were used except that gaseous carbon dioxide was
passed through the solution for 150 minutes, and then replaced by a stream of nitrogen for a further 130
 LI$MI!LUX .LND McINNES: SUCROSIC MONOESTERS 2381

TABLE 1
?'he rates of reaction a t SOo using 4 meq of catalyst
-- --

E x ~ c r i m e n t a ln~~unber:'
1 2 3 -1 D 6 7 8 If 10 11
'rirnle
(min) Percentage of m c t l ~ y lmyristate reacted
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"Four tuilliequivaleots of potassium carbonate, potassil1111~nethosidc,lithit~mmethoside, s o d i ~ ~ rmethoside,

n atlrl potassium
l~ydrosiclein 5 ml anhydrous methanol were used in esperiments 1 and 2, 3 arld 4 . 5. (i,and 7, respectively. Saturated tnethat~olic
solutions of potassium llydroside (4 meq in 0.50 ml methanolic solution) and potassium meLhoside (4 meq in O.GS rnl mctlianolic
solution) were used in esneritnents 8 and 0 , resr~ectively.Saturated aqueous solutions of votassium llydroside (4 meg in 0.26 ml
aoueoui solution) and odtassium carbonate (-4 ~ n e ain0.329 rnl of aiueous solution) were used in esneriments 10 a ~ i d11. re-

, .
I h c effcct of sucrosc concentration on thc rate of reaction a t SO0*
Can. J. Chem. 1962.40:2376-2393.

--
I'crcentage of methyl myristate reacted

, .
l ime
60 mnlolc
s~~crose,
40 mmole
st~crose,
20 nlnlolet
sucrose,
(min) espt. 9 espt. 12 espt. 13

*.A saturated solution of potassium metltoxide in methanol (-I rnecl in 0.68 ml

methat~olicsolution) was used as catalyst.
?Substantial amounts of catalyst ~~rccipitated
fro111solution and rlid noL ~ediasolve
completely during the course of the reaction.

T A B L E 111
T h e elfcct of fatty acid chain length o n the rate of rcaction a t SOo
--
Percentage of methyl cster reacted

7 .
Methyl AIethyl h/Ieth>-l
1 ime myristatc, palmitate, stearate,
(~nin) cspt. 14'" expt. 15" expt. 16"

"Four tnilliequivalents of potassium metl~osidcin 5 ~ n rnetl~a~lolic

l solution \vere
used to form the catalyst.

mint~tes.Potassium carbonate, 4 nleq, in 5 nlI of anhydrous methanol was used as catalyst under con-
ditions for homogeneous catalysis. After 150 minutes thc sucrose myristate yicld was 19.3 and 89.OY0 for
I' and P I , respectively, whereas after 280 m i n ~ ~ t the
e s corresponding vaIucs for P and 1'1 were 84.7 a ~ n d
88.6%, respectively.
 2382 C X X A D I A N J O U R X A L O F C H E M I S T R Y . VOL. -10. 1962

T h e depression of the rate of reaction by gaseous carbon dioxide is shown graphically in Fig. 5.
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Time in Minutes Milliequivalents of Potassium Sucrote

FIG. 5. Rates of transesterification reaction a t 80' using 4 lneq of p o t a s s i ~ ~carbonate

~n under conditions
of homogeneous catalysis. 111 (a) streams of carbon dioxide and nitrogen were passed successively through
the solution, whereas in (b) only nitrogen was used.
FIG. 6. T h e plot of the pseudo first-order rate constants for the standard transesterification reaction
a t 80' against the sucrate concentratio11 in 320 1111 of reaction solution.

The Effect of Catalyst Conce?ztration on the Rate of T~ansesterificationat 80'

Can. J. Chem. 1962.40:2376-2393.

T h e standard transesterification reaction conditions were used except that 0.5, 1.0, 2.0, 4.0, and 8.0 meq
of potassium methoxide in 5 ml of anhydrous methanol were used a s catalyst, respectively. A precipitate
of potassium sucrate was present during the entire reaction when more than 4 meq of potassium ion were
used.
T h e plot of the pseudo first-order rate constants for the reactions a t the different catalyst concentrations
versus the catalyst concentrations is given in Fig. 6.
The Effect of Temperatzrre on the Rate of Transestelificution
The standard transesterification reaction was carried out a t 80' (at 55 mm pressure) and 9 i 0 (at 140 m m
pressure), respectively. Potassium methoside, 2 meq, in 5 ml methanol was used a s a source of catalyst.
T h e pseudo first-order rate constants calculated for the d a t a obtained a t 80' and 97' and plotted in Fig. 7
were 2.36X10-4 and 4.51X10-" sec-I, respectively. Calculation by means of the Arrhenius equation (15)
gave a value of 9.9 kcal mole-' for the energy of activation.

T i m e i n Minutes
FIG. 7. The plot of the logarithm of the methyl n~yristateconcentration against time for the standard
transesterification reaction, a t 80' and 9'i0, using 2 meq of potassium sucrate as catalyst.

Isolation of Sucrose Mono- and Di-mylistate

Three standard transesterification reactions were carried out a t 80' in the absence of n-octadecane and
the sucrose ~nyristatefrom the experiments combined. Four n~illiequivalentsof potassiu~n ~nethoxidein
0.68 n ~ of
l anhydrous metl~anolicsolution was used a s catalyst. T h e products of the reaction were isolated
by taking each reaction solution to dryness, a t 70°, on a rotary evaporator, a t the end of the reaction
period of 150 minutes. T h e residue was then partitioned between n-butanol and 5 % sodiu~nchloride and
the crude sucrose ester isolated a s described above. The co~nbinedcrude product weighed 26.57 g. The
latter was then chromatographed on 250 g silicic acid (Malli~lckrodt)using graded elution \\.ith methanol/
 LEMIEUS ASD M C I N N I ~ SSUCROSE
: MONOESTERS 2383
chloroform solutions. :-\s the chromatogram cle\~elopedthe constituents were visible against a translucent
bacl;grouncl. The separation was also follo\ved by taking infrared spectra of aliquots of the eluant. In this
uray it was possible to isolate three fractions containing methyl myristate, sucrose dimyristate, and sucrose
monomyristate, as shown in Table IV.

TXB1.E IV
Chromatographic separation of sucrose myristates on silicic acid

Volume of \\:eight of
solvent fraction
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Fraction Solvent (ml) (e) Com~ound"

I Chloroform 2000 0.80 h~lethylmyristate
II loc$, ~nethanol/chlorofor~i~ 250 7 .95 Dimyristate
111 loC&methanol/chloroform 1400 17.(iO Sucrose monomyristate
- - - - - - -

"The residue irom fraction I was actually collected i n the first 700 ml of eluant and its i r ~ f r a r e dspectrum was ider~ticalwith
t h a t of a n autllentic sample of m e t l ~ y lmyristate.

T h e sucrose inonomyristate (17.6 g) \\-as precipitated from 100 nil acetone a t -5' to yield 15.6 g of pure
sucrose monomyristate as a white amorphous solid, m.p. 180-186'; [ol]D +36.7' (c, 4.8% in chloroform);
saponification equivalent, 549 (theory, 552). Anal. calc. for C?6H48012:C, 56.50%; H, 8.70y0. Found: C ,
56.36%; H, 8.63%.
The sucrose ditnyristate (7.05 g) was precipitated f r s t from methanol and then from acetone t o yield
6.05 g sucrose dimyristate as a white amorphous solid, m.p. 130-145"; [ o l ] ~t 2 9 . 7 " (c, 5.2% in chloroforrn);
saporiilication equivalent, 376 (theor)., 381). i\na!. calc. for C4OH74013: C, 63.09;; H , 9.77%. F o u ~ l d :C ,
Can. J. Chem. 1962.40:2376-2393.

63.39%; H, 9.91%.
T h e infrared spectra for sucrose mono- and di-myristate were consistent with those expected for a molio-
and di-fatty acid ester of a polyhydric alcohol. The two esters showed considerable differences in the
relative intensities of the OH stretching and C=O stretching vibratio~isa t 3500 and 172.5 c111-I, respectively,
which could be used as a means of identifcatio~i.
Determination of the Eqzrilibriz~nz Conslant IC1
T h e equilibrium constant K l for the reaction
sucrose + sucrose dimyristate + 2 sucrose monomyristate
was estimated as follows a t two different co~icentrationsof sucrose.
Sucrose, 1 m~nole,\\.as dissolved in 15 1111 a ~ i h y d r o ~D~Ms F a t SO0, and 0.2 meq of potassi~~ril metlioxide
in 0 . L n l methanolic solution was added. T h e potassium sucrate \\rhicli precipitated was redissolved by the
addition of 5 ml anhydrous methanol a n d the solution was talcen t o dryness-under reduced pressure. T h e
residue was dried, under reduced pressure over phosphorus pentoxide, for 2 hours. Pure sucrose rnono-
niyristate, 1 mmole, was then added to t h e residue of sucrose and potassium sucrate, and the mixture nlas
dissolved in 15 rnl anhydrous DMF. T h e ho~nogeneousreaction solution was a t a temperature of SOo for
90 mi~iutes.Care was talcen a t all times to exclude moisture from the reaction solution. At the end of t is
period the catalyst was neutralized b y the addition of 1 ml of a D N F solution containing 0.2 meq of potas-
sium l~ydrogenphthalate. After taking the solution to dryness under reduced pressure, the sucrose ~nyristates
were isolated in the Iiianner described above. Chromatography of the sucrose myristates (466.9 mg) on 10 g
silicic acid using graded eli~tionwith ~ n e t h a n o l / c h l o r o f o r solutions
~~~ yielded 336.9 mg (0.61 mmole) of
sucrose monomyristate, and 124.7 nig of sucrose "dimyristate". T h e separation was followed by comparing
the infrared spectra of the sucrose ester in 5-ml fractions of the eluant from the chronlatographic column
with the infrared spectra of pure sucrose mono- and di-myristate. Seventeen fractions of 5% methanol/
chloroform and 15 fractions of 10% methanol/chloroform were collected. T h e first 20 fractions contained
sucrose dimyristate atid the last 10 fractions contained sucrose monomyristate. T h e two intermediate
fractions contained no sucrose ester, indicating that a complete separation of sucrose monomyristate fro111
sucrose di- and higher myristates was achieved. On the assumption that only mono- and di-esters were
formed, the yield of ester was 9470.
A second experiment, carried out under identical experimental conditions except that only 0.5 mmole
of sucrose was used initially, yielded 434.0 mg of sucrose myristate. Chromatography of a s a ~ n p l eof t h e
latter (420.0 mg) on 10 g silicic acid, a s described above, yielded 152.0 mg (0.109 mniole) of sucrose di-
~ilyristateand 267.0 ~ n g(0.483 mmole) of sucrose monomyristate. 'The relative intensities of the hydroxyl
and carbonyl stretching v i b r a t i o ~ ~clearly
s indicated the product to contain some tri- and higher esters. On
the assumption that only mono- and di-esters were formed, the yield of ester was 88%.
An estimate of the eql~ilibriumconstant, K I , for the reaction
sucrose + sucrose dinlyristate F? 2 sucrose ~iionomyristate
 2384 CAN.\DI.\N JOURN.\L O F CIIEMISTIZY. VOL. .40.1963

can be made using the above results and the as sump ti or^ that only morlo- and di-esters \\.ere formed. On
this basis, the yields of tlie esters are corrected to 1007; in order to use the following expression to calculate
the equilibrium constant:
K 1 = [sucrose ~i~onomyristate]?/[sucrose][sucrose
dimyristate]
= 41112/(2Y-z-lII)(Z-llI),
where IVI = nioles of sucrose monon~yristatea t equilibrium, Y = total moles of sucrose in thc system, and
Z = total myristoyl groups in the s y s t e n ~ .
In the first experiment, ill = 0.61X100/94 = 0.65, I' = 2, and Z = 1 ; therefore K l = 2.0. In the
second experiment, ill = 0.483XIOO/S8 = 0.55, I' = I .5, and Z = 1 ; therefore, K 1 = 1.8.
In all subsequent calculatio~isa value of Ii, = 2 \\,as assu~ned,since the error, i n t r o d ~ ~ c eby
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d ignoring
the presence of higher-substituted sucrose myristates, was less for this value.
Tlte Rate of Epz~ilibrationof GI,'-Labelled Sz~c-rose zaitk Sz~croscMono- clnd Di-zttyristate
Uniformly C1"-labelled sucrose, 0.4!)5 mmole, was equilibrated with 0.466 mmole of pure sucrose mono-
myristate, a t SO0, in anhydrous DM17 using 0.1 meq of potassium ~iicthosicleas catalyst. The reaction
solution had a total volume of 5.5 ml and the procedure for preparation of the solutions was identical with
that describccl abovc for tlic solutions usccl to dcterniinc the eq~~ilibrium constant I i l . Alicluots, 1 ml, of
the reaction solution urere talien a t intervals of 10, 30, 45, and 65 minutes and the solvent removecl rapidly
(3 minutes) under reclucecl pressure. The residue was extractecl with three 2-ml aliquots of chloroform ancl
the combined chloroform extract was transfcrrecl c~ua~ltitati\~cly to a small chromatographic column con-
taining 1 g silicic acicl in chlorofor~ii.Elution with 25 1111 10% 1iiet11a1io1/~11lorofor1~i followed by removal
of thc solvcnt, under reduced prcssurc, yielded CH-labcllcd sucrose myristatcs unc-ontaminatccl wit11 C1-l-
labelled sucrose. The chromatographic proceclure for isolating the C1,'-labelled sucrose myristates was
established by taking synthetic mixtures of sucrose monomyristatc and sucrose di-rn>.ristate with C1I-
Can. J. Chem. 1962.40:2376-2393.

labelled sucrose in anh~~clrous D M F , but in the absence of potassium sucratc, and recovering the corre-
sponcling sucrose estcr in q u a ~ ~ t i t a t i vj~iclcl,
c and uncontaminated with Cll-labclled sucrose.
Another cquilibration cspcrimcnt using 0.475 mmolc of sucrosc climyristate and 0.505 mmole sucrose
in the presence of 0.1 meq of potassiuni s ~ ~ c r awas t e carried out under iclentical experimental conditions.
Thc specific activities of thc C14-lal~ellccl sucrose arid sucrosc myristates were determined by converting
the compounds to barium carbonate by tlie apparatus and nlcthod of Calvin (16) cscept that a 0.2 ilf
solution of barium hydrosidc mas usecl instcacl of sodium hydroxide, All samplcs \\,ere counted a t infinite
thickness, using a "Traccrlab (SC-50B) Automatic 1;low Counter", and r c q ~ ~ i r c123.5 d mg of barium
carbonate for a plnnchet having all arca of 4.!J4 cm'. Uncler the experimental conditions ~ ~ s citt l\\:as found
that rnocl; cornbustio~lsgavc a ~legligil~le blanli of lcss than 0.3 nlg of barium carbonate. .-\I1specific activities
wcrc calculated from thc timc take11 for 10.' clisintegrations. Ho\vc\.er, since tlie compositio~lof the sucrose
myristates was not detcrnlinetl, thc spccilic acti\.itics \irere calculated as tlie number of c o u ~ ~per t s mirlr~te
per milligram of barium cnrbonatc (c.p.m./mg BaCOs). T h c C~n-lal)elledsucrose was founcl to Iiavc a
specific activity of 8.475 c.p.m./mg BaCOx.
The theoretical specific acti\.ities of the sucrosc myristates, isolatcd after cquilibration, \\ere calculated
,,
in the following manner. 1he concentrations of sucrose ~norionl).ristate(111) and sucrosc dimyristate were
i n g valucs for I., Z , ancl Ii, into ecluation [I]. For csamplc, these \.slues were
calculated by s ~ i b s t i t ~ ~ t tlic
0.961, 0.466, ar~cl2.0, respectively, for tlie espcrimcnt using 0.495 mmole of C1.'-lal:elled sucrosc ancl 0.466
rnn~oleof sucrose ~nonomyristate. The calculated cquilibriun~concentrations of sucrose mono- ant1 di-
myristate were found to be 0.39 and 0.038 mnrole, rcspective!y. T h e thcorctical specific activity \vas then
calculated from the equation
i1 = 12fsse/(d+n~), ["I
where A \vas the theoretical specific acti\:ity; s" was the specific activity of the o r i g i ~ ~ C1-'-labelled
al sucrose;
s was the total nloles of sucrose in thc sucrose 1110110-and di-~nyristate;f \\as the fraction of the total moles
of sucrose in the original reaction solution, whether present as sucrosc myristate or free sucrose, which
was C1"-labelled; d was tlie ~nolesof barium carbonate obtained on combustion of the sucrose dimyristate;
ancl 112 was the moles of barium carbonate obtained on comb~rstionof the sucrose monon~yristate.
The values of d, nz, f , s, s" in the above experiment were 1.52 nirnole, 10.14 mmole, 0.5236, 0.428 mmole,
and 8475, respectively. Substitution of these \.allies into ecl~~ation [2] gave a value for the theoretical specific
activity, i l , of 1950 c.p.m./~ngB a C 0 3 assuming random distribution of the sucrose ~noleculesin tlie sucrose
myristate.
A similar calculation for the experiment using 0.505 nimole of C1.'-labelled sucrose and 0.475 ~nmole
of sucrose dimyristate gave values for d, ?ir, f , s, and s" of 11.0 mmolc, 10.40 m~nole,0.515, 0.675 m~nole,
and 8475, respectively, and a value of 1650 c.p.m./mg BaCOn for the theoretical specific activity A . The
sucrose mono- and di-~nyristateconcentrations a t equilibrium were calculated to be 0.4 and 0.275 ~ n n ~ o l e ,
respectively.
The theoretical weight yields of the C14-labelled sucrose myristates in 1 ml of tlie reaction solutions
were calculated, a s s u n l i ~ ~co~nplete
g equilibration of the C1"-labelled sucrose and sucrose ester, from the
 LEMIEUX A N D McINNES: SUCROSE MOXOESTERS 2385
eql~ilibrium cot~centratio~lsof Ct"-labelled sucrose 111ono- and di-rnpristate. 'l'he calculated yields were
44.4 and 78.1 mg/ml as compared with the highest experimental yields after 65 minutes' reaction of 38.3
ancl 72.2 nlg/ml, respectively (see Table V).
e s given in Table V.
The results of the equilibration s t ~ ~ d i are
TABLE V
Equilibration of Cl.l-lal~elledsucrose with sucrose ~nononlyristateand sucrose dimyristate a t 80'
-
- -- -
.

Sucrose n~onornyristate" Sucrose dim yristatci

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Yield of Specific activity Yie!d of Specilic activity

Reaction sucrose of sucrose s~lcrose of S L I C ~ O S C
time m).~.istates nlyristates m)~ristates myrista tes
(min) (mg) (c.p.m./mg BaCOa) (md (c.p.m./mg BaCO;)
10 37. I 1216 71.7 1337
30 37.5 1404 70.7 1418
45 38 3 1432
65 38 3 1471
Theoretical specific activit) 1030
-
*Reaction carried out using sucrose mooomyristate and Cl.1-labelled sucrose as reactants.
?Reaction carried out using sucrose dilnyristate and C14-labelled sucrose as reactants.

Thc Effect of ilfethanol Co?~ce?l,tratio?~

on the Estcnt of Reartio?~at SOo
\r standard transesterification reaction \\,as carried out a t SOo using 0.68 1111 of a saturated methanolic
solution containing 4 meq of potassium methoside as catalyst. T\vo a l i q ~ ~ oof t s the reaction ~ n i s t u r ewere
Can. J. Chem. 1962.40:2376-2393.

taken a t intervals ancl the percentage of niethyl myristate which had reactecl in one aliquot (0.6 ml) was
cletermined b y GLI'C using n-octadecane a s an internal standard. The other aliquot (2.0 ml) was tratisferrcd
t o a small, stopperecl test tube (total volume 2.2 ml) and allowed to e q ~ ~ i l i b r aat et 80'. At the end of the
equilibratio~~ period the percentage of methyl ~nyristatewhich had reacted was determined once more. Care
was taken a t all times to exclude moisture from the reaction solutions. T h e r e s ~ ~ lare t s given in Table V1.
'r.\BI,E VI
Effect of ~nethanolconcentration on the extent of r e a c t i o ~a~t SOo

Sample No. 1 2 3 -1 5 6 7
Time (111in)' o 10 20 40 SO 120 150
9; iiiethyl myristate reacted 11.0 7 44.2 65.8 84.2 90.2 94.5
'rime (min) for the reaction to
reach cquilibri~~m 1-1.5 140 130 110 70 30
~nethylm!.ristatc reacted 5 . 62.2 6 . 78.1 90.0 84.5
*Samples \\.ere with~lrawnfrom the reaction mixture a t this tirne both lor analysis and for storage a t 80' in a closed system
to achie\,e equilibrium.

Constu?zt I<?
Deteittzinntiolr of thc Eqzlilibi.i~~?iz
T h e equilibrium constant K ? for the reaction
sucrose + methyl myristatc & sucrose tnyristates + methanol
was deterr~~ined by approaching the equilibrium from both sides of t h e reaction.
A transesterihcatioti reaction solution containing 3.18 mmoles of sucrose, 1.06 mn~oleof methyl 111)ristate,
0.676 mmole of n-octadecane, 1 mmole of methanol, and 0.116 mmole of potassium sucrate ill 17 1111 of
anhydrous D M F solution was brought t o equilibril~ma t SO0 it1 a 17.2-1111 test illbe fitted with a rubber
serum cap. The rate of equilibration was determined by taking, a t intervals, through t h e serum cap, with
a calibrated microsyringe, 0.1-rill aliquots of t h e reaction solution and analyzing for methyl tnyristate by
GLPC using the n-octadecane as an internal standard. I t was assumed that the equilibrium condition had
been reached when there was 110 further decrease in the concentration of methyl myristate. At the end
of the equilibration period 10 mmole of methanol was added t o the reaction solution a n d the solution
analyzed for methyl myristate once more after a n interval of 30 minutes. Since the concentration of methyl
ester showed a significant increase this established that the catalyst was not destroyed during the equili-
bration pried. I t should be noted t h a t care was talcen t o exclude moisture a t all times from the reaction
solution. The rate a t which equilibrium was reached is shown in Fig. 8.
I n another experiment, 1 ~nmoleof sucrose monomyristate, 0.638 mtnole of n-octadecane, 1 mlnole of
methanol, and 0.116 rnmole of potassium sucrate were equilibrated a t 80" in 15 ml of D M F solution con-
tained in 15.1-m1 test tube. T h e rate of equilibration was followed a s described above, and is shown graphir-
ally in Fig. 8.
 CANADIAN JOURNAL O F CHEMISTRY. VOL. 40, 1962

mu
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0
0 60 120 180 240 850
Time in M i n u t e s

FIG.8. The rate of equilibration of sucrose and methyl myristate with sucrose monomyristate and
methanol in D h I F solution a t 80'. For the curve denoted by the reaction solution was 18.75, 6.25, 6.25,
and 0.7X10-2 il/I in sucrose, methyl myristate, methanol, and all;oside ion, respectively, whereas for the
curve denoted by the solution was 6.25, 6.25, and 0.7X10-? 111 in sucrose ~nonomyristate,methanol, and
alkoxide ion, respectively.

The data for the first experiment in Fig. 8 shows t h a t 51.570 (0.549 mmole) of the methyl myristate
had reacted a t equilibrium to form sucrose myristates. If i t was assumed t h a t only sucrose mono- and
di-myristate were formed in the reaction the equilibrium concentration of the former (0.468 mmole) could
be calculated by substituting values for I' (3.18 mmole), 2 (0.549 mmole), and K1 = 2 into equation [I].
Setting R and S as the equilibrium and initial molar amounts of methanol and myristoyl group in the
Can. J. Chem. 1962.40:2376-2393.

reaction solution, respectively, the nlolar amounts of the reactants and products in the reaction a t equi-
librium are, sucrose monomyristate = M, sucrose dinlyristate = ( 2 - M ) / 2 , methanol = R, sucrose =
(2 Y-Z-11[)/2, and methyl myristate = X - 2 . The other variables (Y, 2 , and iM) were defined previously
in connection with equation [I]. The equilibrium constant, K P ,can be calculated from the expression
K P = [sucrose myristates'~[n~ethanol(/[sucrose][methyl
myristate]
= R(iVI+2)/(2Y-2-M)(X-2).
A value of 0.577 for K Pis obtained on substituting values (in mmole) for Y (3.18), S (1.06), il/I (0.468),
R (1.549), and 2 (0.549).
In the same \\lay, the values (in mmole) of Y ( I ) , X ( I ) , M (0.31), R (0.472), and 2 (0.472) which were
obtained in a second experiment gave a value of 0.576 for K?. In this experiment 52.8% (0.528 mmole)
of the lnyristoyl group was converted to methyl myristate (see Fig. 8). Consequently, the methanol con-
centration (R) a t equilibrium was 0.472 mmole, and 47.2Y0 of methyl mpristate had reacted to form sucrose
myristate (see Fig. 8).
A solution of 60 n~molesucrose, 20 nlmole methyl myristate, and 12.75 mmole n-octadecane in 300 nll
D M F was maintained a t 80' and 75 mln pressure, for 6 hours, with nitrogen passing through the solution.
No catalyst was added to the reaction mixture. Analysis of the reaction solution by GLPC a t 30-minute
intervals revealed that the methyl myristate concentration remained constant over the entire reaction
period.
The P r e p a ~ a l i o ?of~ Sucrose fiIyristalcs on a Preparatiue Scale
As a consequence of the kinetic studies of the reaction the following preparative procedure was developed.
Sucrose (60 mmole) was dissolved in anhydrous D i a F a t 80' and 65 nlm pressure with vigorous and
continuous stirring, and with a stream of nitrogen passing through the solution. After about 15 minutes
the sucrose was completely dissolved and the solvent refluxed to a point in the Vigreaus column about 2
inches from the neck of the flask. Sodium methoside solution (4 ml containing 4 meq) was added below
the surface of the solution sing a hypodern~icsyringe, in the usual manner. The evolution of nlethanol
was rapid but caused no difficulties. After equilibrium was re-established, the oil-bath temperature ~ v a s
raised to 100°, whereupon the solution achieved a temperature of 80" and refluxed about half way up the
Vigreaus column. The still head temperature was about 50". The system was kept under these conditions
for a further 15 minutes and then the methyl myristate (20 mmole) was added using a hypodermic syringe.
The solution was then maintained a t 80' for 150 minutes. During this reaction period approxi~nately50 n ~ l
of the D M F distilled over slowly.
At the end of the reaction period, glacial acetic acid (0.5 1111) was added to the stirred reaction solution,
a t atmospheric pressure, to stop the reaction. The solution was then talcen to dryness a t 70°, under reduced
pressure, in 30 minutes, and the sucrose mpristate isolated by partitioning the residue between n-butanol
and 570 sodium chloride solution as described above. The residue of sucrose myristate (9.6 g) was then
precipitated fro111 acetone to yield sucrose ~nyristates(9.2 g) as a white powder. Theory for pure sucrose
monomyristate is 11.0 g.
 LEMIEUX A N D McINNES: SUCROSE MONOESTERS 2387

DISCUSSION
Before the kinetic study of the transesterification reaction could be carried out it was
first necessary to develop analytical lnethods for determining the rates and extents of
the reaction, and the sucrose mono- and di-ester content in the product of the reaction.
The rates of reaction were deterlnined by followiilg the collcentration of the methyl
esters of the higher fatty acids in the reaction solution by GLPC using n-octadecane as
an internal standard of constant concentration. In this way it was established that the
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co~lcentrationof methyl ester could be determined to within &2y0 froin 10 to 100%

of the range of concei~trationsencountered (see Fig. 1). i\/Iethyl inyristate was used for
inost of the Icinetic studies since it had been used in this laboratory for previous investi-
gations (5) and had a convenient retention volume relative to n-octadecane. Although
Lovelocli (17) had shown that the response of the ionization detector was not the saiile
for hydrocarbons and methyl esters of fatty acids, due to differences in the magnitude
of their ionizatioil potentials, the methyl esters of myristic, palmitic, and stearic acids
gave the same molar response as n-octadecane under our experimental conditions.
Although the catalyst was not neutralized before the product of reaction (sucrose
ester) was isolated, the simple routine procedure which was developed gave high, repro-
ducible yields of sucrose ester for reactions carried out under identica! experimental
Can. J. Chem. 1962.40:2376-2393.

conditions (see Table I). I t was found, however, that the addition of an equivalellt
anlount of acetic acid or potassium hydrogen phthalate neutralizes the catalyst without
causing any significant inversion of sucrose or sucrose ester.
Of the other analytical methods used, one worthy of mention is the separation of
sucrose monoester from higher esters of sucrose by chromatography on silicic acid using
methanol/chloroform solutions as the developing phase. The recoveries were quantita-
tive.
Equipped with these experimental procedures and analytical tools, we undertook a
kinetic investigation of the reaction. I t see~neddesirable to begin with an examination
of the procedure recommended by the Snell Laboratories (2, 6). Reactions performed
by this procedure at 80' and initiated by the addition of solid potassium carbonate
proceeded a t unpredictable rates and to variable extents (see Fig. 3). I t became evident
that this situation was to an important degree dependent on the rate of dissolution of
the catalyst since the rate of reaction was substantially increased (about twofold) by
using very finely divided potassium carbonate distributed over Celite (see Fig. 3 ) . Also,
although the solid potassiun~carbonate did not dissolve completely in any of our experi-
ments, it was apparent that variable amounts went into solution. The observatiolls
suggested that the rate and extent of dissolution of potassiuin carbonate were related to
the presence of traces of water. In fact, the rate of reaction and yields of sucrose ester
were influeilced by the addition of water to the reaction solution (see Fig. 4). The exact
nature of this effect was not established since it was later observed that homogeneous
solutions of potassiu~ncarbonate in D M F or D M F containing sucrose could catalyze
the formation of sucrose ester. These results suggested that a satisfactory solution to
the problem would require conditions for hornogeneous catalysis. Furthermore, identical
speciinens of the reagents were used for all experilneilts dealing with one reaction variable,
since it was realized that different specimens of the reagents would be used during the
investigation, which could affect the reproducibility of the results. In this way it was
possible, for example, to compare the rates of reaction, even if they were not the absolute
reaction rates, within a selected group of experiments.
 2388 CANADIAN JOURNAL O F CHEMISTRY. VOL. 40. 1962

I t was decided, therefore, to add the potassium carbonate as a solution in methanol. At

this point a surprising (to us) observation was made. When a saturated methanolic
solution of potassium carbonate was prepared, under reflux, the titration of the solution
revealed the presence of strong base. Furthermore, the amount of strong base increased
the longer the solution was heated. I t was apparent, therefore, that heating led to the
loss of acid through the evolution of carbon dioxide. By analogy the reaction of sucrose
with potassium carbonate should lead to the formation of potassium sucrate in high
concentration. The formation of sucrose myristate using solid sodiu~nhydride as the
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catalyst suggested, moreover, that sucrate ion was the reactive species which catalyzed
the reaction. Consequently potassiun~methoxide should serve to initiate the catalysis
a t least as efficiently as ~ o t a s s i u mcarbonate.
The procedure for the transesterification reaction was therefore modified t o enable
methanolic solution of the catalyst to be added to the reaction n~ixture.T h e methanol
was then removed by distillation, under reduced pressure, to leave a homogeneous
reaction solution. I t was now found that the reaction proceeded a t highly reproducible
rates, and these were independent of the base used (see experiments 1-6, Table I). Fur-
thermore, the infrared spectra of sa~nplesof sucrose ester (see experiments 1-4, Table I )
were identical, indicating that the product composition was the same. The rates of
reaction using the conditions for homogeneous catalysis were much superior to those
Can. J. Chem. 1962.40:2376-2393.

obtained by other workers (2, 5, 6, 8, 9).

I t was also demonstrated that aqueous solutions of potassium carbonate and hydroxide,
or methanolic solutions of potassiuin hydroxide, led to the formation of detectable
amounts of potassiuin soap, resulting in lower rates of reaction and yields of sucrose
ester (see experiments 7, 8, 10, and 11, Table I). Superior initial rates of reaction were
observed when a saturated solution of potassiu~ninethoxide was used (see experiments
9 , 12; Tables I and 11, respectively) insteacl of a dilute methanolic solution of potassiun~
methoxide (see Table 111) to catalyze the reaction. These results indicate that d r y methanol
is the solvent of choice for the preparation of potassium sucrate solutioi~s,and t h a t the
discrepancy in the initial rates of reaction was related t o the efficiency with which
methanol was being removed from the reaction solution. This latter effect will, of course,
be Inore critical in the initial stages of the reaction when the methanol concentration is
highest, and is consistent with the observation of Ko~noriand his associates (9) that
the rate of transesterification increased when the pressure in the system was decreased.
Under our experimental conditions a rapid and reproducible rate of removal of methanol
could not be achieved by distillation alone. I-Iowever, the introduction of a rapid rate of
stirring, combined with a continuous stream of nitrogen as a carrier gas, was found to
positively solve this problem, and this use resulted in highly reproducible rates of re-
action. Moreover, the viscous nature of saturated methanolic solutions of potassium
methoxide made thein difficult to handle. Consequently, most of our experiments were
carried out using dilute methanolic solutions.
The effectiveness of the procedure for the removal of the methanol from the reaction
solution was tested by taking samples, a t intervals, fro111 a transesterificatio11 reaction
and equilibrating then1 in sealed glass tubes a t the reaction temperature. T h e data in
Table VI clearly illustrate the necessity for efficient removal of methanol fro111 the
reaction solution. Furthermore, in view of the high rates of reaction obtained using our
standard transesterification conditions it can be concluded that inethanol was being
removed rapidly in all of our experiments in which conditions for homogeneous catalysis
prevailed.
 LBMIEUS A N D MCINNES: SUCROSE MONOESTERS 2389

Experiments directed a t obtaining a direct measure of the equilibrium constant for

the reaction
sucrose + methyl myristate F? silcrose ester + methanol
were carried out by approaching the equilibrium from both sides (see Fig. 8). The equi-
librium constant, Kq, for this reaction was foul~dto have a value of 0.57 in both cases.
The close agreement is probably fortuitous, although it is not considered liliely that
the actual value will differ significantly from this value. This result is consistent with
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the observations of Fehland and Adlcins (18) and Juvet and Wachi (19) that the forma-
tion of methyl ester is favored in reactions in which aliphatic alcohols are equilibrated
with the methyl esters of fatty acids using base (18) or acid (19) catalysis.
I t became obvious, early in the investigation, that the transesterificatio~l reaction
followed pseudo first-order liiiletics in the methyl ester of the fatty acid (see Fig. 7).
Evidence that sucrate ion was the reactive species which catalyzed the reaction was
provided when it was observed that sodium hydride catalyzed the reaction, and when
the extent and rate of reaction, using a methanolic solutio~lof potassium carbonate as
catalyst, was strongly depressed when a stream of carbon dioxide was passed through
the solution instead of the usual nitrogen (see Fig. 5 ) . This requires that sucrose (SOII)
and potassium carbonate react according to the following scheme,
Can. J. Chem. 1962.40:2376-2393.

SOH + I<zCOs F! I<.OS + ICHC03,

SOH + I<HCOs F? I<.OS + H?CO3,

to form potassium sucrate (K.OS). Furthermore, the fact that equivalent amounts of
potassiunz carbonate, potassium methoxide, sodium methoside, and lithium methoxide
gave identical rates of reaction call only be explained satisfactorily if sucrate ion is the
effective catalyst for the reaction (see Table I).
The transesterification reaction m ~ ~ therefore
st be bimolecular and involve nucleo-
philic attacli of the methyl ester by sucrate ion, as would be expected from the earlier
studies (13) on the ~nechanismof base-catalyzed traiisesterificatioi~s.

SOH
SO-I<+ + CHJOH ---\ CH30-I<+
0
II
SO-C-R

In view of this mechanism, the rate of the transesterification reaction should be

dependent only on the concentrations of sucrate ion and methyl ester. However, the
actual rate of reaction would also depend on the rate of re-forination of the methyl
ester ill the reverse direction, and this will depend 011 the efficierlcy with which the
inethanol is removed from the reaction solution. Since the inethanol is kept a t an insig-
nificant low level under our experimental conditions (see above), the sucrate ion con-
centration should remain a t virtually constant level throughout the course of the reaction.
 2390 CANADIAN JOURNAL OF CHEMISTRY. VOL. 40. 1962

Thus, the rate of reaction should be directly proportional to the sucrate ion concentra-
tion. I t can be seen from Fig. 6 that this is the case for reaction solutions which were
up to 3.125X10-3 116 in potassium sucrate (1 ineq of potassium sucrate per 320 ml of
reaction solution). At higher concentrations of potassium sucrate the reactions behave
in a non-ideal manner, and solid potassium sucrate precipitates froill solution a t con-
centrations in excess of 12.5X lop3 mole liter-' (4 ineq of potassiunl sucrate per 320 1111
of reaction solution).
T h e downward drift may result from the association of the ionic substance a t high
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concentrations in such a manner as to reduce the effective concentration.

In view of the above considerations the rate of reaction should be independent of the
concentration of sucrose a s long as methanol is being removed effectively. This was
found to be the case and no appreciable rate difference was observed by doubling or
halving the initial sucrose concentration (see Table 11). Although the rate and extent
of reaction was somewhat lower a t the lowest concentration of sucrose (see experiment
13, Table 11), it was observed that a precipitate of potassium sucrate was present during
the entire reaction period. In view of the high rate of reaction, however, it is felt that
if all the catalyst had been ill solution the rates of reaction of the three concentrations
of sucrose would have been identical. This is in contrast to the results of Komori and
co-workers (9, l l ) , who claiill that the rate of reaction was dependent on the sucrose
Can. J. Chem. 1962.40:2376-2393.

concentration.
T h e chain length of the fatty acid (see Table 111) and the nature of the cation have
little effect on the rate of reaction. In the latter case, equivalent amounts of potassiu~n
carbonate, lithium methoxide, sodium methoxide, and potassiuin methoxide, as potential
sources of sucrate ion, gave essentially the saine rates of reaction (see Table I ) . The only
possible gain that could be obtained by changing the cation would be in the solubility
of the metal sucrate in the reaction solution. I t was observed that lithium sucrate was
the only catalyst which did not give an initial precipitate when it was added to the
reaction mixture. The saturation levels of the rnetal sucrates, other than potassium
sucrate, were not deternzined. These results are in contrast to the cation-sucrose complex
theory of worlters a t the Herstein Laboratories, which must necessarily predict different
rates of reaction for the different cations (7, 8).
Illspectioil of Fig. 6 reveals that the effective sucrate ion concentration is only 1.5 meq
per 320 ml of reaction solution (4.96 X lop3mole liter-') when the pseudo first-order rate
constant has a value of 2.36X 10-"ec-' a t the 2 meq level of potassium sucrate. Conse-
quently, the corresponding second-order rate constant (k,) for the reaction a t 80' has
a value of 5.03X10-3 inole liter1. Froill this value for k, and the energy of activation
(9.9 ltcal mole-I), the Arrhenius frequency factor (0.7X 10j liter mole-I sec-l) was calcu-
lated (15). Using the transition-state theory (20), the following constants were calculated,
AFY = 22 ltcal mole-I, AH* = 9 ltcal mole-', and AS* = -38 entropy units. T h e low
frequency factor and large negative entropy is usually associated with reactions in
which there is electrorestriction of the solvent inolecules due to the formation of a highly
polar activated complex (21, 22). Reactions which exhibit this behavior also have negative
voluines of activation, and the rates of reaction are accelerated by pressure (22). These
phenomena are observed in the acid and base hydrolysis of esters and amides (23-25),
and in the transesterification of esters with an alcohol using base catalysis (13, 26).
IJsing chromatographically pure samples of sucrose monon~yristate,it was possible
to establish the equilibrium constant IC1 for the reaction
sucrose + sucrose dill~yristate2 2 sucrose monomyristate
 LEMIEUS A N D MCINNES: SUCROSE MONOESTERS 2391

to be approximately 2. Although the equilibrium was not approached from both sides,
the values of K 1 were obtained a t two different sucrose concentrations. The above ex-
pression neglects the fornlation of tri- or higher myristoyl sucroses. Our chrolllatographic
analyses definitely indicate that such compounds are formed. However, their concen-
trations seemed negligible when two or more moles of sucrose were used per mole of
lllyristoyl group.
The theoretical yield of sucrose monomyristate (M) corresponding to any initial
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concentration of sucrose (Y) and methyl myristate ( 2 ) could be determined from a

knowledge of K1 provided it was assumed that there was quantitative conversion of
the methyl myristate to sucrose mono- and di-myristate. Using a value of K 1 = 2, the
quadratic equation [I] gave two solutions for M , only one of which was positive, namely,
M = d ( Y 2 + 2 YZ-Z2- Y).

If Y and M were expressed as multiplies of 2 (i.e., Z = l), the above equation reduced
to
M = d ( Y 2 + 2 Y - 1 - Y).
Since this equation was satisfied by all values of Y fro111 0.5 to co, the effect of sucrose
concentration on the yield of sucrose monomyristate could be shown graphically by
Can. J. Chem. 1962.40:2376-2393.

plotting M / Z versus Y/Z. I t should be noted, however, that this equation is only valid
when an equilibriunl exists exclusively between sucrose, sucrose dimyristate, and sucrose
monomyristate. At concentrations of sucrose which are low relative to myristoyl group
content substantial amounts of higher-substituted nlyristoyl esters of sucrose will be
fornled in their equilibrium proportions. Therefore, this equation can only be given
values for Y/Z >, 2 for which the concentration of sucrose esters with more than two
nlyristoyl groups is not significant. Finally, the plot of M / Z against Y/Z must necessarily
pass through the origin, as shown in Fig. 9.

FIG.9. T h e plot of t h e molar ratio of sucrose 1110110111yristate/1netIlyl

myristate (lll/Z) expected by
calculation for the standard transesterificatio~~reaction conditions a t 80° against t h e initial molar ratio
of sucrose/methyl nlyristate ( Y / Z ) .

From Fig. 9, it can be seen, for example, t h a t 0.74, 0.80, and 0.83 mole of sucrose
monomyristate are formed when 3, 4, and 5 moles of sucrose are used per nlole of methyl
myristate in the transesterification reaction. This corresponds to a 92, 93.7, and 95%
yield of sucrose nlyristate (sucrose mono- a n d di-myristates), respectively, a t the three
sucrose concentrations. Thus, it is clear that little is gained by the use of a sucrose to
methyl ester ratio greater than 3. However, in all of our experiments carried out under
conditions for homogeneous catalysis (see Table I , experiments 1-4) the methyl myristate
 2392 CANADIAN JOURNAL O F CHEMISTRY. VOL. 40. 1962

had reacted to the extent of approximately 92y0 and gave a yield of sucrose myristates
of approximately 83y0 by weight. Fro111 equation [l] it can be calculated that, under
our standard conditions, 92% reaction would give 0.80 and 0.06 mole of sucrose mono-
and di-myristates, respectively, corresponding t o a theoretical weight yield of sucrose
myristates of 87y0, and a yield based on the amount of methyl inyristate which had
reacted of 94%. Furthermore, the preparative procedure which was developed as a
result of our kinetic studies gave a yield of sucrose myristate of 84%. The experimental
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yields obtained during our investigations are therefore in excellent agreement with the
predicted yield of 87%.
I t was also established, using uniformly C14-labelled sucrose, that the rate of the
exchange reactions
sucrose* + sucrose dimyristate & sucrose myristates*
and
sucrose + sucrose monomyristate & sucrose myristates*

was too rapid to expect any product control through kinetic control. I n other words,
a t any time during the transesterification reaction, the product prevailing is the thermo-
dynamic product under the conditions which prevail. From Table V it can be seen that
Can. J. Chem. 1962.40:2376-2393.

approximately 6.330% of the theoretical activity was present in the isolated sucrose
myristates after only 10 minutes' reaction. The discrepancy between the specific activity
of the sucrose ester isolated after 65 minutes and the theoretical value is undoubtedly
due to the presence of polysubstituted esters of sucrose. I t is clear from these results
that the sucrose esters formed in the transesterification reaction will have a higher
sucrose monoester content in the initial stages of the reaction than a t the completion
of the reaction. We have not tested this prediction but make it with confidence. This
is in direct contrast to the claims of other workers (2, 5-8) that the reaction proceeds
by way of the rapid for~nationof sucrose diester. Further~nore,any claims that water
(6) and the catalyst concentration (7, 8) influence the product conlposition are clearly
not justified.
The fact that the rate constants for the transesterification remain virtually constant
over the reaction period would suggest that little or no catalyst is used up in side
reactions. The absence of soap in our reaction products is consistent with this observa-
tion. This is in contrast to the results of other workers who report that the catalyst is
used up during the reaction, and that soap is formed in significant amounts (2, 5-8). The
reason for this apparent discrepancy in the experimental results undobutedly lies in
the fact that anhydrous conditions prevailed during this investigation, whereas the
reaction solutio~lsof other workers contained nloisture.

ACICNOWLEDGMENTS
The authors wish to thank the Sugar Research Foundation, Inc., New York, for
sponsoring this research as their Project 88.

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4. SUCROSE ESTERSURFACTANTS. Sugar Research Foundation Inc., New York. 1960.
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