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37
URING T H E L A S T T E N Y E A R S , rearranged lard has water. F r e e alcohol and acid are formed. 3. Saponi-
D become a v e r y i m p o r t a n t shortening ingredient.
I t is p r e p a r e d f r o m n a t u r a l lard by redistribut-
fication is the splitting of an ester by alkali. Soap and
alcohol are formed. 4. Alcoholysis is a displacement of
ing the f a t t y acid radicals among the triglyceride the alcohol radical o f an ester by another alcohol.
molecules. 5. Acidolysis is a displacement of the acid radical of
That esters can exchange acid groups has been an ester b y another acid.
]Known for almost one h u n d r e d years. I n 1865, Friedel
and Crafts, of F r i e d e l - C r a f t s reactions fame, heated Interesterification of Triglycerides
a m i x t u r e of a m y l acetate and ethyl benzoate at F a t s have three ester linkages per molecule. There-
300~ in a sealed tube. W h e n they analyzed the fore the interchange possibilities are many. Not only
contents of the tube, they found ethyl acetate and can the f a t t y acid groups exchange positions within
a m y l benzoate as well as the original a m y l acetate the molecule, but each f a t t y acid can also trade places
and ethyl benzoate (1). This classical experiment was with a n y one of three f a t t y acids in another molecule:
the first demonstration of interesterification~ the ex-
change of aeyl and alkyl groups between esters: Interesterification within Molecules
R C O O R ' + R " C 0 0 R ' " ~ R C O O W " -4- R " C O O R ' CH2OCOR' CH2OCOR" CH~OCOR'
I n this discussion the t e r m interesterification will I t I
CHOCOR'r ~-- CHOCORr ~ CHOCOR"
r e f e r only to an exchange of acid or alcohol groups I ! t
by esters. This is sometimes also called ester inter- CHo.OCOR'" CH2OCOR" CH~OCOt~"
change or transesterification. Although we are p r i m a r - Interesterification between Molecules
ily concerned with the interesterifieation of edible fats,
it will be necessary to refer to a n u m b e r of related CH2OCOR~ CH2OCOR" CH2OCOPJ' CH2OCOR"
ester reactions f r o m time to time. 1. Esterificatio~ is r I I I
CHOCOR,' + CHOCOR" ~-- CHOCOR' W CHOCOR"
the f o r m a t i o n of an ester and w a t e r f r o m an alcohol I t r ]
and acid. 2. Hydrolysis is the splitting of an ester b y Ctt~OCOI~' C H ~ O C O R " C H 2 O C O R " CH~OCOR'
NOVEMBER, 1960 BRAUN: INTERESTERIF1CATIONOF EDIBLE 599
p e r a t u r e catalysts. I t seems likely that these materials r a n d o m endpoint if the f a t is allowed to crystallize
are actually precursors of the real catalyst, which d u r i n g the reaction. The t r i s a t u r a t e d glycerides crys-
p r o b a b l y is a compound of the alkali metal and a tallize first. This removes them f r o m the reaction and
glyceride. According to Eckey, compounds of sodium upsets the equilibrium of the liquid phase, which in
with nmterials much more acidic t h a n alcohol will not t u r n forms more trisaturates in an effort to regain
bring about interesterification at low temperatures. equilibrium. This continues until most of the satu-
The alcoholates are the most convenient to use, and rated acids have been precipitated. Eckey was able
sodium methoxide is the most p o p u l a r of these. Spe- to get 19% t r i s a t u r a t e d glycerides f r o m cottonseed
cial precautions are necessary when the alkali metals oil, which contains 25% s a t u r a t e d acids. I f this f a t
and hydrides arc used, because hydrogen is liberated. had been r a n d o m l y interesterified, it would have
W h e n sodium amide ages, it m a y f o r m nitrogen ox- contained only about 1.5% t r i s a t u r a t e d glycerides
ides which can detonate spontaneously (18). Sodium and more t h a n 40% disaturated mono-unsaturated
methoxide is easier to handle, but its use also requires glycerides.
care because the reaction between water and sodium Directed interesterification has also been used to
methoxide is very exothermic. There have been in- separate d i s a t u r a t e d mono-unsaturated glycerides. To
stances where open containers have ignited in moist accomplish this, catalyst was added to chilled oils in
atmospheres. which most of the crystals were disaturated mono-
The use of sodium methoxide for low-temperature u n s a t u r a t e d glycerides. These served as nuclei for
lard interesterification has been patented (19,20). the f o r m a t i o n of more of the same crystals (25,26).
P a t e n t s have also been g r a n t e d for its use in p r e p a r - N o n r a n d o m interesterification has m a n y possibili-
ing other shortenings (21,22), as well as confectionery ties. A m o n g them are the p r e p a r a t i o n of shortenings,
fats which contain coconut oil (23,24). I t has a num- confectionery fats, and m a r g a r i n e s (16)' as well as
ber of advantages over the old high-temperature the removal of saturated f a t t y acids from oils. IIow-
methods. The reaction ~.an be carried out in ope, i ever as with r a n d o m interesterification, the p r i m a r y
kettles, equilibrium is reached more quickly, and application at the present time is concerned witb the,
the d a n g e r of thermal damage to the f a t is greatly p r e p a r a t i o n of lard shortening. R a n d o m l y r e a r r a n g e d
reduced. Howew..r high- and low-temperature inter- lard is softer and has a lower melting point t h a ,
esterifications have the same effect on glyceride com- conventional shortening. Consequently it has to he
position, crystal structure, and creaming properties firmed u p with about 10% of t r i s a t u r a t e d glyeerides.
if they are continued nntil a r a n d o m equilibrium W i t h directed interesterifieation the t r i s a t n r a t e d glyc-
exists. erides are one of the reaction products. The resultant
F a t s which are to be interesterified should be low f a t also has a better plastic range because it is lower
in moisture, free f a t t y acids, peroxides, and other in disaturated mono-unsaturated glycerides (27).
extraneous materials which will react with sodium Directed interesterification is relatively slow because
methoxide. The catalyst concentration should be kept of the lower t e m p e r a t u r e s used and the time required
as low as practicable to p r e v e n t excessive losses re- for crystallization. Solid catalysts like sodium metal
sulting f r o m saponification by the sodium radical and and sodium methoxide tend to become coated, which
m e t h y l ester formation by the methyl radical. L a r d slows down the reaction still more. This coating effect
which has been filtered and v a c u u m dried but not has been overcome by the use of a dispersion of liquid
refined requires about 0.20% sodium methoxide. sodium-potassium alloy. These liquid spherical parti-
The f a t should take on a reddish brown hue a few cles slough off the coating as it is formed, and as a
minutes a f t e r the catalyst has been added. This color result the f a t is always exposed to active catalyst (27).
p r o b a b l y is due to the sodium-glyceride compound A f t e r the catalyst has been added, the lard is sent
believed to be the true catalyst. I f it does not appear, t h r o u g h a series of heat exchangers to lower the tem-
more catalyst is required. I n the t e m p e r a t u r e range p e r a t u r e gradually. The course of the reaction can
of 60 to 85~ the reaction reaches equilibrium within be followed b y cloud-point determinations. W h e n the
t h i r t y minutes a f t e r the color change occurs. W i t h desired a m o u n t of trisaturates has been formed, the
m a n y fats either the melting point or cloud point catalyst is destroyed. This is done while the f a t is
can be used to follow the reaction. W i t h lard these still in a semisolid state because a n y rise in tem-
determinations are of no value since interesterifieation p e r a t u r e while the catalyst is active will reverse the
changes the melting point of lard only slightly. There- reaction. W a t e r plus carbon dioxide has been recom-
fore cooling curves or single point dilatometrie meas- mended to reduce saponification (27). After the cata-
urements are generally used. The cooling curve of lyst has been destroyed, the f a t is melted so t h a t the
lard has a characteristic h u m p which disappears a f t e r soaps can be removed.
interesterification.
A f t e r the f a t has been interesterified, the catalyst ICIonoglycerides
m a y be inactivated either with water or acid. W h e n lV[onoglycerides m a y be p r e p a r e d either by the ester-
w a t e r is used the saponified acids can be removed with ification of f a t t y acids with glycerol or the glycerolysis
conventional refining equipment. The alkaline water of triglycerides. Glycerolysis is generally used for the
also removes most of the color bodies formed d u r i n g p r e p a r a t i o n of food grade emulsifiers.
the reaction. I f the fat is to be used as a food, the
methyl esters must be removed. These come out read- CH2OH CH2OCOR CH2OCOR CH2OCOR
ily d u r i n g steam deodorization.
CHOH § C H O C O R __~ C H O H + CHOCOR
Directed Interesterification I I --I I
CH20H CH2OCOR CH2OH CH2OH
A r a n d o m a r r a n g e m e n t of f a t t y acids is not always glycerol tri- mono- diglyceride
the most desirable one. E c k e y (17) f o u n d t h a t inter-
esterification can be directed away f r o m its usually Both alcoholysis and interesterification occur. At
NOVEMBER, 1960 BRAUN: I N T E R E S T E R I F I C A T I O N OF E D I B L E 601
[TH[N TIlE PAST FEW Yb'ARS all of us in the fats our bodies are unable to synthesize and, in addition,
W and oils i n d u s t r y have become acutely aware
of the research indicating a relationship be-
to (tarry into our tissues the fat-soluble vitamins which
are so imporlarlt to health. Lipid materials, of which
tween heart disease and dietary fats. Besides the fats are one class, are importarlt constituents of all
potential effects on our markets, these p r o g r a m s arc living (.'ells and life as we know it would be impossible
of vital concern in ternls of the health of the nation, without these f a t t y materials. Thus, there is no doubt
our families, and ourselves. that fats are excellent foods.
This is a controversial tel)it and an a(qive area of Ihlwew~r, recent clinical studies have clearly shown
research. There are i m p o r t a n t differe,wes between that there arc i m p o r t a n t differences in the way in
experimental animals and h m n a n beings in the ways which our bodies metabolize fats f r o m different sources
iu which blood vessels react to the (tietary factors and that these differences m a y be associated with the
presumed to lead to atheroselerosis and heart disease, development of coronary heart disease.
Therefore available data are inconclusive to the ex- Oue of the bits of evidence linking heart disease with
tent that they provide at least some degree of s u p p c r t dietary fats has come fronl population and epidemi-
for each of several points of view. clerical studies. Statistics are being amassed in all
My purposes in the present review are to outline the p a r t s of the world on local incidences of various dis-
nature of the evidence now available, to indicate the eases, the foods people eat, and the conditions u n d e r
limitations in the data, and to discuss the interpreta- which they live. There are v e r y serious limitations to
tions and hypotheses on which c u r r e n t clinical re- the accuracy of such data and consequently they m u s t
search is based. be i n t e r p r e t e d with caution. F o r example, medical rec-
F i r s t of all, there is no doubt that fats are excellent ords from the United States are not directly compar-
foods. They are highly concentrated sources of energy able to those from I n d i a where few people ever see a
and contribute much to the enjoyment we get out of doctor. In addition, reliable d i e t a r y histories are dif-
our meals. As a m a t t e r of fact a certain amount of fat ficult to obtain so the information available generally
is necessary to provide the essential f a t t y acids which relates to the quantities of food available in the mar-