Reduced calorie triglyceride mixtures

Fat mixtures enriched with triglycerides having long, saturated, preferably C.sub.16 to C.sub.22, fatty acid residues and short, preferably C.sub.2 to C.sub.4, acid residues are employed in edible compositions as low calorie fats. The preferred embodiments comprise mixtures of at least two triglycerides bearing long residues (e.g. stearyl) and short residues (e.g. acetyl or propyl). In one preferred embodiment, each triglyceride contains short chain residues which are different from those in the other triglyceride. In another preferred embodiment, at least a portion of the triglycerides have two different short residues. Methods of using the low calorie fats and food products incorporating them, particularly in coating, shortening and margarine products, are disclosed.

TECHNICAL FIELD 
This invention relates to the use of low calorie triglyceride mixtures in 
edible compositions. 
Dietary fat is the most concentrated source of energy of all the nutrients, 
supplying 9 kcal/gram, about double that contributed by either 
carbohydrate or protein. The amount of fat in the American diet has 
increased in the last 60 years by about 25% (Mead, J., et al. Lipids, 
Plenum, New York, 1986, page 459), so that fats now provide approximately 
40% (or more) of the daily caloric intake. 
Fat contributes to the palatability and flavor of food, since most food 
flavors are fat-soluble, and to the satiety value, since fatty foods 
remain in the stomach for longer periods of time than do foods containing 
protein and carbohydrate. Furthermore, fat is a carrier of the fat-soluble 
vitamins, A, D, E, and K, and the essential fatty acids, which have been 
shown to be important in growth and in the maintenance of many body 
functions. Hence, major research efforts have focused on ways to produce 
food substances that provide the same functional and organoleptic 
properties as fats, but not the calories. Synthetic fats have been created 
and are now undergoing testing for safety. Unfortunately, many consumers 
are concerned with the synthetic connotation of food additives of this 
type and will not avail themselves of the advantages they offer. 
There is a need for a fat which is low in calories and high in 
functionality, but is not perceived as artificial. 
BACKGROUND ART 
The most abundant group of fats are triglycerides--esters of fatty acids 
with glycerol (1,2,3-propanetriol). Natural fats have a broad range of 
functionalties and are handled in different ways by the human digestive 
process. 
Early studies reported that triglyceride fats having high melting points 
were less digestible (Deuel, H. J., The Lipids, vol. II, Interscience 
Publishers, 1955, pages 218 to 220). Later investigators questioned the 
relationship between digestibility and melting points, and scrutinized 
instead the chain lengths and degree of unsaturation of fatty acid 
substituents; straight chain, saturated fatty acids having 4 up to 10 
carbon atons were completely digested by rats, those having 10 to 18 
carbons progressively less digested, and those having 18 or higher only 
slightly absorbed, while monounsaturated acids were about the same as 
saturated acids having 6 carbons (Carroll, K. K., J. Nutr. 64: 399-410 
(1957) at 408). 
In other triglyceride metabolic studies in man only limited areas of 
predictability could be found. In one study a coconut oil fraction 
containing predominantly saturated, long chain triglycerides bearing 89% 
stearic (C.sub.18) and 11% palmitic (C.sub.16) acid residues were absorbed 
31%, compared to 98% for corn oil (Hashim, S. A., and Babayan, V. K., Am. 
J. Clin. Nutr. 31: S273-276 (1978)). However, it was found that increasing 
the stearic acid content of dietary fat did not per se decrease 
absorbability; rather, absorbability could be decreased by increasing the 
amount of tristearin present (i.e., triglycerides having three stearic 
residues; see Mattson, F.H., J. Nutr. 69: 338-342 (1959)). To this 
observation were added the findings that, in the presence or absence of 
dietary calcium and magnesium, stearic acid was well absorbed by rats when 
esterified on the 2-position of triglycerides having oleic acid at the 1- 
and 3-positions, but absorption decreased when a second stearic was added 
to the 1-position (Mattson, F., et al., J. Nutr. 109: 1682-1687 (1979), 
Table 3, page 1685). Stearic acid in the 1-position was well absorbed from 
triglycerides having oleic in the 2- and 3-positions in the absence, but 
not in the presence, of dietary calcium and magnesium (ibid.). When 
stearic was in both the 1- and 3-positions, absorption decreased with or 
without dietary calcium and magnesium, but the effect was more pronounced 
when calcium and magnesium were sufficient (ibid.). 
The digestibility of palmitic acid has also been studied. Palmitic acid was 
better absorbed by rats when situated at the 2-positions of triglycerides 
than at the 1- or 3-positions in naturally occurring fats commonly fed to 
infants, and total fat absorption was adversely influenced by increasing 
the palmitic and stearic acid content in the 1- and 3-positions 
(Tomerelli, et al., J. Nutr. 95: 583-590 (1968)). 
While triglycerides high in stearic acid are less well utilized than 
others, they also tend to be high melting. Tristearin is a solid at room 
temperature; the alpha form is a white powder that melts at 55.degree. C., 
which, on solidification, reverts to the beta form that melts again at 
72.degree. C. The melting points of 1,3-distearin with short or medium 
chain fatty acids at the 2-position are high (Lovegren, N. V., and Gray, 
M. S., J. Amer. Oil Chem. Soc. 55: 310-316 (1978)). Symmetrical 
disaturated triglycerides of stoario acid and/or palmitic, often with 
oleic at the 2-position, melt fairly uniformly near body temperature, and 
this property is of advantage for cocoa butter and hard butter substitutes 
(see, for example, U.S. Pat. No. 4,364,868 to Hargreaves, U.S. Pat. No. 
4,839,192 to Sagi, et al., and U.S. Pat. No. 4,873,109 to Tanaka, et al.), 
and for hardstocks for margarines and shortenings (see, for example, U.S. 
Pat. No. 4,390,561 to Blair, et al., U.S. Pat. No. 4,447,462 to Tafuri and 
Tao, U.S. Pat. No. 4,486,457 to Schijf, etal., U.S. Pat. No. 4,865,866 to 
Moore, and U.S. Pat. No. 4,883,684 to Yang). Because of their 
functionality, high melting, high stearic fats have limited applications 
in food compositions requiring more plastic or liquid triglycerides. 
Fats have been prepared by substituting acetic acid for a portion of the 
fatty acids occurring in ordinary fats or oils, thus producing 
triglycerides bearing short acetyl and long substituents. For saturated 
fats high in stearic acid, the substitution of acetyl groups for a portion 
of the stearyl groups lowers the melting point. These acetoglycerides were 
investigated during the 1950's and found to be digestible. Feeding studies 
indicated that the nutritive value of mono- and diacetin fats were 
essentially the same to animals as those fed the corresponding 
conventional triglycerides (Mattson, F. H., et al., J. Nutr. 59: 277-285 
(1956), although acetooleins were more digestible than acetostearins 
(Ambrose, A. M., and Robbins, D. J., J. Nutr. 58: 113-124 (1956) and 
animals grew poorly when fed acetostearin as the sole dietary fat 
(Coleman, R. D., et al., J. Amer. Oil Chem. Soc. 40: 737-742 (1963)). 
While lower melting than tristearin, acetostearins still have high melting 
points, limiting applications in food products requiring plastic or liquid 
fats. In fact, though melting points of compounds structurally related 
generally decrease with decreasing molecular weight (and mono- and 
distearins having medium to long saturated substituents follow this rule), 
the melting points of triglycerides in the C.sub.18 C.sub.n C.sub.18 and 
C.sub.n C.sub.n C.sub.18 series, where n=2 to 6, anomalously show the high 
molecular weight C.sub.6 (caproic acid) mono- and distearin derivatives to 
have the lowest melting points and the low molecular weight C.sub.2 
(acetic acid) mono- and distearin derivatives to have the highest 
(Jackson, F. L., et al., J. Amer. Chem. Soc. 73: 4280-4284 (1951) and 
Jackson, F. L., and Lutton, E. S., J. Amer. Chem. Soc. 74: 4827-4829 
(1952); see also the data in Example 38). Plastic fats containing 
acetostearins suggested for use as shortenings and the like were 
formulated to contain significant levels of unsaturated fats and typically 
employed significant levels of fatty acids which would yield high 
saponification numbers or were liquid at room temperature (U.S. Pat. No. 
2,6714,937 to Baur and Lange (1952) and Baur, F. J., J. Amer. Oil Chem. 
Soc. 31: 147-151 (1954)). 
Acetostearins are waxy fats having sharp melting points. In contrast to 
fats bearing medium and/or long substituents, acetostearins also exhibit 
unusual polymorphism (ibid., and Feuge, R. O., Food Technology 9: 314-318 
(1955)). Because of their melting and crystal properties, the fats have 
been suggested as useful for coating food products such as meat, fish, 
cheese, and candy (U.S. Pat. Nos. 2,615,159 to Jackson and 2,615,160 to 
Baur). Compositions of this nature are often referred to as "hot melts" 
and may contain antibiotics (U.S. Pat. No. 3,192,057 to Hines and Shirk) 
or polymeric materials (U.S. Pat. No. 3,388,085 to Levkoff and Phillips) 
to to prolong the life of the coating. 
The short chain fatty acids, acetic, propionic, and burytic acid, also 
called, as a group, volatile fatty acids, occur in the large intestine of 
all mammalian species so far studied (Cummings, J. H., Gut 22: 763-779 
(1981)). Except for a small percentage of butyric acid in milk fat (i.e., 
about 3.5 to 4%), volatile fatty acids rarely occur in nature esterified 
to glycerol in fats, but are, instead, generally free by-products of 
fermentation in the gut. Physically, short chain fatty acids "are not at 
all `fatlike` in character; in fact they are hydrophilic substances with 
complete miscibility with water" (Bailey's Industrial Oil and Fat 
Products, 4th. ed., J. Wiley, New York, 1979, volume 1, pages 16 to 17). 
Early reports investigating the metabolism of short acids and triglycerides 
bearing short chain residues showed no regular relationship between 
nutritional value and the number of carbon atoms in the fat (Ozaki, J., 
Biochem. Z. 177: 156-167 (1926) at 163). For example, when fed to rats at 
levels of 5% and 10% of the diet, triacetin and tributyrin were 
nutritious, yielding weight gains in the top 20 to 25% of the fats tested, 
whereas tripropionin and triisovalerin were toxic (ibid.). In 1929, 
Eckstein reported that rats fed trioloin and sodium butyrate grew at the 
same rate (J. Biol. Chem. 81: 163-628 (1929) at 622). 
In 1935, L. E. Holt, et al., observed that infants fed milk enriched with 
tributyrin retained more fat per day (90.1 to 90.2%) than those in a 
butterfat control group (88.9%); the study concluded that absorption was 
favored by fatty acids with relatively short chains (J. Ped. 6: 427-480 
(1935), Table VIII, page 445, and Conclusions, number 4, page 477). 
Similar results were obtained with triacetin, with absorption of 
tributyrin and triacetin reportedly superior to that of corn oil, although 
corn oil yielded higher calories (Snyderman, S. E., et al., Arch. Dis. 
Childhood 30: 83-84 (1955)). Substitution of triacetin, tripropionin, or 
tributyrin for half the glucose and starch in a rat diet did not 
significantly affect the digestible, metabolizable or net energy 
measurements, but lower body weight gains were observed in animals fed 
tributyrin in two experiments and triacetin in one experiment (McAtee, J. 
W., et al., Life Sci. 7: 769-775 (1968)). 
In in vitro digestibility studies, tributyrin is readily cleaved by 
pancreatic lipase. Data measuring lipolysis as a function of chain length 
show tributyrin much more rapidly hydrolyzed than other substrates (see 
Sobotka, H., and Glick, D., J. Biol. Chem. 105: 199-219 (1934), comparing 
triglycerides bearing three identical C.sub.4 to C.sub.18 acyl groups, and 
Desnuelle, P., and Savary, P., J. Lipid Res. 4: 369-384 (1963), comparing 
triglycerides bearing three identical C.sub.2 to C.sub.18 acyl groups), 
although some reports rank tripropionin slightly better (Weinstein, S. S., 
and Wynne, A. M., J. Biol. Chem. 112: 641-649 (1936), comparing 
triglycerides bearing three identical C.sub.2 to C.sub.6 acyl groups, and 
Wills, E. D., in Desnuelle, P., ed., The Enzymes of Lipid Metabolism, 
Pergamon Press, New York, 1961, pages 13 to 19, comparing triglycerides 
bearing three identical C.sub.2 to C.sub.18 acyl groups). In fact, because 
tributyrin is such a good substrate and because the triglyceride is 
sufficiently water-soluble to allow enzymatic measurements in a 
homogeneous solution, it is often selected as a lipase substrate standard 
(Ravin, H. A., and Seligman, A. M., Arch. Biochem. Biophys. 42: 337-354 
(1953) at 353). 
Other lipase preparations readily cleave short chain triglycerides. 
Tributyrin was found to be hydrolyzed with the greatest initial velocity 
by human milk lipase, while pig liver lipase hydrolyzed tripropionin and 
tributyrin with an equal initial velocity much greater than any other in a 
study comparing C.sub.2 to C.sub.18 triglycerides (Schonheyder, F., and 
Volqvartz, K., Enzymologia 11: 178-185 (1943)). Tributyrin was hydrolyzed 
more readily than C.sub.6 to C.sub.18 triglycerides by human milk bile 
salt-activated lipase (Wang, C. S., etal., J. Biol. Chem. 258: 9197-9202 
(1983)). A liver lipase hydrolyzed trivalerin the fastest, with tributyrin 
the second fastest (Sobotka and Glick, cited above). 
In contrast to triglycerides bearing long chain (.about.C.sub.16 to 
C.sub.24) fatty acids and those bearing short chain fatty acids, medium 
chain triglycerides, generally obtained from kernel oils or lauric fats 
and encompassing those substituted with C.sub.6 to C.sub.12, predominantly 
C.sub.8 to C.sub.10, fatty acids, have been of particular interest because 
they are more rapidly absorbed and metabolized, via a different catabolic 
route than those bearing long chain fatty acids (see a recent review by 
Babayan, V. K., in Beare-Rogers, J., ed., Dietary Fat Requirements in 
Health and Development, A.O.C.S. 1988, chapter 5, pages 73 to 86). Hence, 
medium chain triglycerides have been employed in premature infant formulas 
and in the treatment of several malabsorption syndromes (ibid.). Feeding 
studies by H. Kaunitz, et al., demonstrated the usefulness of medium chain 
triglycerides in weight maintentance and obesity control in rats (J. Amer. 
Oil Chem. Soc. 35: 10-13 (1957)). 
Several research groups have exploited the physical and nutritional 
properties of medium chain fatty acids by suggesting that triglycerides 
having stearic and/or behenic acid in combination with medium chain 
substituents be used as low calorie fats (Eur. Pat. Ap. Pub. No. 322,027, 
corresponding to U.S. application Ser. No. 132,400, to Seiden, who defined 
medium chain substituents as comprising C.sub.6 to C.sub.10 residues, and 
Jap. Pat. Pub. No. 2-158,695 to Yoshida, et al., who defined medium chain 
substituents as comprising C.sub.4 to C.sub.12 residues. The latter 
publication, however, exemplified only trace amounts of C.sub.4 fatty 
acids, and suggested incorporating 0 to 1 long chain, unsaturated residues 
as well.) Low calorie triglyceride mixtures having stearic acid at the 
1-position and medium and unsaturated residues in the other positions have 
also been suggested (U.S. Pat. No. 4,832,975 to Yang). 
The polymorphism of triglycerides bearing medium and long moieties 
generally resemble fats bearing long moieties in that they tend to have a 
stable beta crystal structure. This contributes to graininess of fat 
mixtures containing them, and, in chocolate compositions, to the 
appearance of bloom. The preparation of smooth blends require careful 
substituent selection and/or tempering. It would be desirable to have low 
calorie fat mixtures free of this disadvantage. It would also be desirable 
to have a fat which was a true triglyceride but which delivered a minimum 
of calories and exhibited functionalities which permitted use in a wide 
variety of products. 
DISCLOSURE OF THE INVENTION 
An object of the present invention is to provide a new group of low calorie 
triglycerides and food compositions incorporating them. 
It is a principal object of this invention to provide natural low calorie 
fats. 
It is a further object of this invention to provide reduced calorie fats 
having excellent organoleptic properties and functional characteristics 
useful in a wide variety of foods. 
These and other objects are accomplished by the present invention, which 
provides mixtures enriched with triglycerides having both long, saturated, 
preferably C.sub.16 to C.sub.22, fatty acid residues and short, preferably 
C.sub.2 to C.sub.4, acid residues. These mixtures are employed in edible 
compositions as low calorie fats. Most preferably, the long fatty acid 
residues will be C.sub.18 and the short acid residues will be C.sub.2 to 
C.sub.3. 
Denoting the aliphatic portion of the long fatty acid substituent as L and 
the short as S, the mixtures are enriched with one or more SSL, SLS, LLS, 
and LSL species described by the following formulae: 
##STR1## 
where each R, independently, is a long chain saturated fatty acid residue 
having between 16 and 40 carbons, preferably 18 to 22 carbons; 
and 
each R', independently, is a short chain acid residue having 2 to 5 
carbons, preferably 2 to 4 carbons, most preferably 2 to 3 carbons. 
Depending upon the preparative procedure (to be more fully described 
below), the mixtures may also contain triglycerides of the formulae 
##STR2## 
where R and R' are as defined above. 
However, preferred mixtures contain essentially no SSS and preferably less 
than 2%, more preferably less than 1%, LLL. 
As depicted above, the triglycerides employed in this invention are 
compounds consisting of three molecules of the same or different acids 
esterified to glycerol, 1,2,3-propanetriol, having the formula (CH.sub.2 
OH).sub.2 CHOH. The acids are short C.sub.2 to C.sub.5 acids, or long and 
saturated C.sub.16 to C.sub.40 acids. 
One preferred embodiment is a mixture of at least two of the above 
described triglycerides, at least one bearing two different short residues 
as R' groups. Another preferred embodiment is a mixture of at least two 
triglyceride fats each bearing a similar array of long, saturated residues 
but a different complement of short chain residues. 
Methods of using the low calorie fats and food products incorporating them 
are also disclosed. The low calorie triglycerides of this invention are 
especially advantageous in coating fat compositions comprising at least 
about 75%, preferably at least about 85%, more preferably at least about 
90%, by weight SSL and SLS species and between about 0.1 and about 25%, 
preferably between about 5 and about 10%, by weight LLS and LSL species. 
In chocolate confections, preferred embodiments are employed in amounts 
effective to reduce bloom. 
The low calorie triglycerides of this invention are also especially 
advantageous in margarine and shortening fat compositions. Preferred 
shortening fat embodiments contain at least two triglyceride species 
bearing long, saturated acid residues and propionic acid, buryrio acid, 
mixtures of acetic acid and propionic acid, mixtures of acetic acid and 
buryrio acid, mixtures of propionic acid and buryrio acid or mixtures of 
acetic acid, propionic acid, and butyric acid residues. Preferred 
margarine fat embodiments are trans-free and contain 1 to 95%, preferably 
5 to 75%, low calorie fats and 5 to 95%, preferably 25 to 95%, edible oil

EXAMPLES 
The following examples are presented to further illustrate and explain the 
present invention and should not be taken as limiting in any regard. 
Unless otherwise indicated, all parts and percentages are by weight, and 
are based on the weight at the particular stage of the processing being 
described. Ratios of short to long (S/L) acid substituents are mole 
ratios. 
Nuclear magnetic resonance (NMR) data reported are proton NMR data. NMR S/L 
ratios are determined as the ratio of intensities of the methyl 
(--CH.sub.3) resonances for the short and long fatty acid groups, 
respectively, obtained by dividing the integral areas attributable to S 
components by the areas attributable to the L, and have experimental 
errors of 5 to 10%. In a typical NMR spectrum at 300 MegaHertz or higher, 
the long acid methyl resonance occurs farthest upfield, at .about.0.9 ppm, 
as a triplet. The short acid methyl resonance is structure dependent and 
occurs at .about.2.00 ppm (acetyl groups), .about.1.15 ppm (propionyl 
groups) and .about.0.95 ppm (butyryl groups). 
Differential scanning calorimetry (DSC) is used to obtain information about 
the melting and crystallization behavior of reduced calorie triglycerides. 
A liquid sample is cooled from about 20.degree. C. above its melting point 
to about 20.degree. C. below, held at the final temperature, and then 
reheated to the initial temperature. Crystallization and melting 
thermograms are subjected to several analyses. The melting point(s) are 
taken as the peak minima (endothermic transition in the down direction of 
the chart plotting mW per unit time versus temperature) obtained in the 
heating cycle, and the crystallization temperature as the peak onset in 
the cooling cycle. Enthalpies of phase transitions are automatically 
calculated in mJoules/mg of sample by choosing the two temperature points 
of onset of melting and 100% melted. For compound mixtures prepared from 
natural oils, it is useful to calculate, by integration, a solid fat index 
in which the percent liquid portion of the sample is calculated for any 
temperature. As described hereinafter, this method is employed where 
A.O.C.S. Methods Cd 16-81 or Cd 10-57 are not used. 
Example 1 
Acetyl-distearoyl glyceride (sometimes commonly called acetyl distearin), 
which comprises a mixture of 1-acetyl-2,3-distearoyl glyceride (SLL) and 
2-acetyl-1,3-distearoyl glyceride (LSL), 
##STR13## 
and which may be used as a component of the fat compositions of this 
invention, is prepared in this example. 
One gram of distearin, obtained commercially from Sigma Chemical Co., is 
charged to a 100 mL round-bottomed flask equipped with a magnetic stir 
bar, a reflux condenser, a thermometer, and a heating mantle. To this is 
added an excess (15 mL) of acetic anhydride (95%, Aldrich Chemicals), and 
the mixture is heated to reflux with constant stirring for three hours. 
After cooling to ambient temperature, the mixture is transferred into a 
separatory funnel using 75 mL diethyl ether. 
The solution is washed alternatively with 10% sodium bicarbonate and water 
until it is neutral to litmus. Finally, the sample is dried at 90.degree. 
C. for one hour. Analysis of DSC (differential scanning calorimetry) data 
shows the sample to be 100% solid at 80.degree. F., 98% solid at at 
92.degree. F., and solid at 100.degree. F. 
Example 2 
Other component fats, namely, propionyl-distearoyl glyceride (sometimes 
commonly called propionyl distearin), a mixture of 
1-propionyl-2,3-distearoyl glyceride and 2-propionyl-1,3-distearoyl 
glyceride, which have the following structures, 
##STR14## 
and butyryl-distearoyl glyceride (sometimes commonly called butyryl 
distearin), a mixture of 1-butyryl-2,3-distearoyl glyceride and 
2-butyryl-1,3-distearoyl glyceride, which have the following structures, 
##STR15## 
may be prepared by substituting propionic anhydride and butyric anhydride, 
respectively, for acetic anhydride in the esterification of distearin as 
outlined in Example 1 above. 
Example 3 
This example illustrates the preparation of another fat, diacetyl-stearoyl 
glycerol (sometimes commonly called stearoyl diacetin), a mixture of 
1,2-diacetyl-3-stearoyl glyceride and 1,3-diacetyl-2-stearoyl glyceride, 
which have the following structures, respectively: 
##STR16## 
One gram of glycerol monostearin, obtained commercially from Spectrum 
Chemicals, is charged to a 100 mL round-bottomed flask equipped with a 
magnetic stir bar, a reflux condenser, a thermometer, and a heating 
mantle. An excess (15 mL) of acetic anhydride (obtained from Aldrich 
Chemicals) is added, and the mixture heated to reflux for three hours with 
constant stirring. After cooling to ambient temperature, the mixture is 
transferred to a separatory funnel using 75 mL diethyl ether. 
The solution is washed alternately with 10% sodium bicarbonate and water 
until it is neutral to litmus and then dried at 90.degree. C. for one hour 
to afford a mixture of triacylglyceride structures. 
Example 4 
This example illustrates alternative syntheses of acetyl-distearoyl 
glyceride prepared and illustrated in Example 1 above and 
diacetyl-stearoyl glyceride prepared and illustrated in Example 3 above. 
To 90 mg (0.14 moles) 1,3-distearin is added 5 mL acetyl chloride, and the 
mixture is stirred and heated to 85.degree. C. until all the acetyl 
chloride is reacted. An additional 2 mL acetyl chloride is added and the 
mixture is reheated to yield predominantly 2-acetyl-1,3-distearoyl 
glyceride. 
A mixture of 2.1 g (0.01 mole) stearoyl chloride and 1.4 g (0.01 mole) 
monoacetin obtained from Kodak is heated to 85.degree. C. for 2 hours. 
Another 4.0 g stearoyl chloride is added and the mixture is reheated to 
yield predominantly 1-acetyl-2,3-distearoyl glyceride. 
To 100 mg (0.28 moles) monostearin is added about 5 mL acetyl chloride, and 
the mixture is stirred and heated to 80.degree. C. in a reaction flask for 
an hour to yield predominantly 1,2-diacetyl-3-stearoyl glyceride. 
Example 5 
Other component fats, namely, dipropionyl-stearoyl glyceride, a mixture of 
1,2-dipropionyl-3-stearoyl glyceride and 1,3-dipropionyl-2-stearoyl 
glyceride, which have the following structures, respectively, 
##STR17## 
and dibutyryl-stearoyl glycerol, a mixture of 1,2-dibutyryl-3-stearoyl 
glyceride and 1,3-dibutyryl-2-stearoyl glyceride, which have the following 
structures 
##STR18## 
may be prepared by substituting propionic anhydride and butyric anhydride, 
respectively, for acetic anhydride in the esterification of monostearin as 
outlined in Example 3 above. 
Example 6 
In this example, 1,2-dibutyryl-3-stearoyl glyceride (depicted above), a 
triglyceride component that may be employed in the mixtures of this 
invention, is prepared using an alternate synthetic route employing 
tributyrin and methyl stearate (Akoh, C. C., and Swanson, B. G., J. Amer. 
Oil Chem. Soc. 66: 1581-1587 (1989)). 
A 250-mL, 3-neck flask fitted with a temperature probe, stopper, and vacuum 
outlet is charged with 52 g (.about.0.17 moles) of tributyrin and 52 g 
(.about.0.17 mole) methyl stearate. The mixture is warmed to 
48.degree.-50.degree. C. Sodium (2.3 g) is heated in 100 mL xylene to 
remove sodium oxides and then added to the warmed mixture, causing 
vigorous bubbling. Vacuum is applied, and the mixture is gradually heated 
to 110.degree. C. The solution becomes yellow, then amber, and, after 
about 40 minutes, very viscous. Heat is removed, and the reaction mixture 
is cooled and extracted with hexane (100 mL), ethyl acetate (200 mL), 
acetic acid (5 mL), hydrochloric acid (10 mL), and (200 mL) water (200 
mL). The organic layer is washed twice with salt water (100 mL), dried 
over magnesium sulfate, filtered, and concentrated to obtain a clear, pale 
yellow oil. The product is purified on a silica gel column eluted with 
hexane and hexane/ethyl acetate (20:1, v/v). 
Example 7 
A reduced calorie triglyceride fat mixture of 1-acetyl-2,3-distearoyl 
glyceride, 1,3-diacetyl-2-stearoyl glyceride 2-acetyl-1,3-distearoyl 
glyceride, and 1,2-diacetyl-3-stearoyl glyceride is prepared in this 
example. 
One gram of glycerol monostearin and distearin, obtained commercially from 
Stephan Chemicals is charged to a 100 mL round-bottomed flask equipped 
with a magnetic stir bar, a reflux condenser, a thermometer, and a healing 
mantle. An excess of acetic anhydride (15 mL, Aldrich Chemicals) is added, 
and the mixture heated to reflux with constant stirring for three hours. 
After cooling to ambient temperature, the mixture is transferred to a 
separatory funnel using 75 mL diethyl ester. 
The solution is washed alternately with 10% sodium bicarbonate and water 
until it is neutral to litmus, and then dried at 90.degree. C. for one 
hour to give a mixed triacylglyceride composition. 
Example 8 
Other reduced calorie fat mixtures, such as (i) dipropionyl-stearoyl 
glyceride and propionyl-distearoyl glyceride, a mixture of 
1,2-dipropionyl-3-stearoyl glyceride, 1,3-dipropionyl-2-stearoyl 
glyceride, 1-propionyl-2,3-distearoyl glyceride, and 
2-propionyl-1,3-distearoyl glyceride, and (ii) dibutyryl-stearoyl 
glyceride and butyryl-distearoyl glyceride, a mixture of 
1,2-dibutyryl-3-stearoyl glyceride, 1,3-dibutyryl-2-stearoyl glyceride, 
1-butyryl-2,3-distearoyl glyceride, and 2-butyryl-1,3-distearoyl 
glyceride, may be prepared by substituting propionic anhydride and butyric 
anhydride, respectively, for acetic anhydride in the esterification of 
monostearin and distearin as outlined in Example 7 above. 
Example 9 
In this example, a triglyceride mixture comprising acetyl-stearoyl 
glycerides of the formulae 
##STR19## 
where the R groups are predominantly --(CO)(CH.sub.2).sub.16 CH.sub.3 is 
prepared. 
A 3-L, 3-neck reaction flask equipped with a heating mantle, stirrer, 
thermometer and reflux condenser is charged with 1140 g technical grade 
(.about.40%) monostearin obtained commercially from Stephan, Maywood, N.J. 
S.F.C. (supercritical fluid chromatography, a quantitative method more 
completely described in Example 21 below) analysis of the starting 
material reveals 50% monoglyceride, 27% diglyceride and 23% triglyceride. 
The starting material is melted, 360 g acetic anhydride (.about.98% pure, 
obtained from Aldrich Chemicals) is added, and the mixture is refluxed 
under vacuum for 12 hours. During the course of the reaction, 195 g of 
clear acetic acid is removed. 
The golden honey-colored product is purified using a falling-film still at 
180.degree. C., &gt;1 mm Hg to yield a light, soft solid. This is further 
purified using steam deodorization at 180.degree. C., &gt;1 mm Hg to yield 
1113 g (86.3%) bright yellow solid having a capillary melting point of 
53.degree. C. NMR analysis shows an S/L ratio of 0.9. S.F.C. analysis 
(more fully described in Example 21 below) shows 50% of the total 
composition to comprise SSL/SLS, 35% LSL/LLS, and 8.4% LLL (with 0.5% 
monoglycerides and 5.2% diglycerides). 
Example 10 
In this example, a propionyl-stearoyl glyceride mixture comprising LSS, 
SLS, LLS, LSL, and LLL components having the formulae 
##STR20## 
where R' is --(CO)--CH.sub.2 CH.sub.3 and 
R is --(CO)(CH.sub.2).sub.16 CH.sub.3 
is prepared. 
A 3-L, 3-neck reaction flask equipped with a heating mantle, stirrer, 
thermometer and reflux condenser is charged with 1110 g technical grade 
monostearin obtained commercially from Stephan (which contains mono-, di- 
and triglycerides as described in Example 9 above). The starting material 
is melted, 437 g propionic anhydride (.about.99% pure, obtained from 
Aldrich Chemicals) is added, and the mixture is refluxed at 160.degree. C. 
for about 15 hours. The mixture is then distilled at 180.degree. C. &lt;100 
mm Hg to remove propionic acid. 
The product is then purified using a falling-film still at 180.degree. C. 
and deodorized at &lt;1 mm Hg, 50 mL H.sub.2 O, 170.degree. C. to yield 1171 
g (90.8%) of a soft solid having a capillary melting point of 54.degree. 
C. NMR analysis shows the S/L ratio is 0.9. S.F.C. analysis (more fully 
described in Example 21 below) shows the final product contains 55% 
SSL/SLS, 33% LSL/LLS, and 8.2% LLL (with the remainder comprising 0.5% 
monoglyceride and 3.3% diglyceride). 
Example 11 
This example describes the preparation of another propionyl-stearoyl 
glyceride mixture like the one described in Example 10 above, except that 
different proportions of SSL, SLS, LLS, LSL, and LLL components are 
formed. 
A 3-L 3-neck reaction flask equipped with a heating mantle, stirrer, 
thermometer and reflux condenser is charged with 914 g technical grade 
monostearin obtained commercially from EM Chemicals (Lot # 3006101). 
S.F.C. analysis of the starting material reveals 54.2% monoglycerides, 
37.7% diglycerides and 8% triglycerides. The starting material is melted, 
670 g propionic anhydride (.about.99% pure, cbtained from Aldrich 
Chemicals) is added, and the mixture is refluxed at 180.degree. C. for 12 
hours. The mixture is then distilled at 25 mm Hg to remove propionic acid. 
The product is then purified using a falling-film still at 180.degree. C., 
&lt;1 mm Hg and deodorized at 0.5 mm Hg, 45 mL H.sub.2 O, 180.degree. C. to 
yield 924 g (77%) of a brown soft solid. NMR analysis shows the final 
product to have an S/L ratio of 1.2. 
Example 12 
This example describes an alternate preparation of dipropionyl-stearoyl 
glyceride (depicted in Example 4 above and as SSL and SLS in Examples 10 
and 11 above). 
A 3-L 3-neck reaction flask equipped with a heating mantle, stirrer, 
thermometer and reflux condenser is charged with 915 g monostearin 
obtained commercially from Spectrum Chemicals (.gtoreq.90% pure, Lot # 
EF027). The starting material is melted, 697 g propionic anhydride 
(.about.99% pure, obtained from Aldrich Chemicals) is added, and the 
mixture is refluxed for 18 hours. The mixture is then distilled at &lt;100 mm 
Hg, 180.degree. C. to remove propionic acid. 
The product is purified using a falling film still at 180.degree. C., &lt;1 mm 
Hg, and deodorized at 0.5 mm Hg, 50 mL H.sub.2 O, 180.degree. C. to yield 
1074 g (89.5%) of a clear orange liquid. NMR analysis shows the S/L ratio 
is 2.1. Analysis of DSC data shows 85% solids at 50.degree. F., 56% solids 
at 70.degree. F., 8% solids at 80.degree. F., and 0% solids at 92.degree. 
F. 
Example 13 
This example describes an alternate preparation of dibutyryl-stearoyl 
glyceride, SLS/SSL triglyceride mixture components depicted in Example 5 
above. 
A distearin starting material is first prepared. A 3-L, 2-neck reaction 
flask equipped with a heating mantle, thermometer, stirrer, and reflux 
condenser is charged with 248 g stearic anhydride (0.45 moles, obtained 
from Aldrich) and 37 g glycidol (0.5 moles). The mixture is stirred and 
heated to 95.degree.-100.degree. C. for 3 hours, 3.2 g tetraethylammonium 
bromide is added, and the is mixture stirred and heated for another 3 
hours at 100.degree.-105.degree. C. DL-2-amino-1-propanol (2.4 g) is added 
and the flask is cooled until it solidifies (.about.65.degree. C). The 
reaction flask is placed in a 60.degree.-65.degree. C. oven, held for 48 
hours, and then heated to melt the product for transfer into a 4-L beaker. 
The product is crystallized from acetone, washed and dried. A 85% yield of 
a &gt;93% pure product is obtained. 
A 3-L, 3-neck reaction flask equipped with a heating mantle, stirrer, 
thermometer and reflux condenser is charged with 530 g of the distearin 
starting material. This is melted, 144 g butyric anhydride (.about.99% 
pure, obtained from Aldrich Chemicals) is added, and the mixture is 
refluxed at 180.degree. C. for 8.5 hours. The mixture is distilled at &lt;100 
mm Hg, 200.degree. C. to remove butyric acid. 
The product is purified using a falling-film still at 180.degree. C., &lt;1 mm 
Hg and steam deodorized at 0.35 mm Hg, 180.degree. C. to yield 545 g (91%) 
of a light brown solid having a capillary melting point of 37.degree. to 
38.degree. C. NMR analysis shows the S/L ratio is 0.6. 
Example 14 
In this example, a butyryl-stearoyl glyceride mixture comprising LSS, SLS, 
LLS, LSL, and LLL components having the formulae 
##STR21## 
where R' is --(CO)--(CH.sub.2).sub.2 CH.sub.3 and 
R is --(CO)(CH.sub.2).sub.16 CH.sub.3 
is prepared. 
A 3-L, 3-neck reaction flask equipped with a heating mantle, stirrer, 
thermometer and reflux condenser is charged with 1078 g technical grade 
(.about.40%) monostearin obtained commercially from Stephan (which 
contains mono-, di- and tristearin as described in Example 9 above). The 
starting material is melted, 507 g butyric anhydride (.about.97% pure, 
obtained from Aldrich Chemicals) is added, and the mixture is refluxed at 
175.degree. C. for about 15 hours. The mixture is then distilled to remove 
butyric acid. 
The product is then purified using a falling-film still at 120.degree. C., 
&lt;1 mm Hg, and steam deodorized at &lt;1 mm Hg, 50 mL H.sub.2 O, 180.degree. 
C. to yield 1173 g (90.8%) of a soft beige final product having a 
capillary melting point of 45.degree. C. NMR analysis shows an S/L ratio 
of 0.9. S.F.C. analysis (more fully described in Example 21 below) shows 
56.4% SSL/SLS, 30% LSL/LLS, and 8.7% LLL (with 4.9% diglycerides). 
Example 15 
This example describes the preparation of another butyryl-stearoyl 
giyceride mixture like the one described in Example 14 above. 
A 3-L, 3-neck reaction flask equipped with a heating mantle, stirrer, 
thermometer and reflux condenser is charged with 864 g technical grade 
monostearin obtained commercially from EM Chemicals (Lot # 3006101, 
described in Example 11 above). The starting material is melted, 770 g 
butyric anhydride (.about.99% pure, obtained from Aldrich Chemicals) is 
added, and the mixture is refluxed at 180.degree. C. for about 12 hours. 
The mixture is then distilled to remove butyric acid. 
The liquid product is purified using a falling-film still and steam 
deodorized at 0.35 mm Hg, 40 mL H.sub.2 O, 180.degree. C. to yield 924 g 
(77%) of a brown soft solid. NMR analysis shows an S/L ratio of 1.2. 
Example 16 
This example describes the preparation of another butyryl-stearoyl 
glyceride mixture like the ones described in Examples 13 and 14 above. 
A 3-L, 3-neck reaction flask equipped with a heating mantle, stirrer, 
thermometer and reflux condenser is charged with 864 g monostearin 
obtained commercially from Spectrum Chemicals (.gtoreq.90% pure, Lot # 
EF027). The starting material is melted, 770 g butyric anhydride 
(.about.97% pure, obtained from Aldrich Chemicals) is added, and the 
mixture is refluxed at 155.degree. C. for about 16 hours. The deep 
orange-red mixture is then distilled to remove butyric acid. 
The milky golden liquid product is purified using a falling-film still and 
steam deodorized at &lt;1 mm Hg, 50 mL H.sub.2 O, 180.degree. C. to yield 
1041 g (87%) of a yellow golden liquid having a white precipitate. NMR 
analysis shows an S/L ratio of 2.0. Analysis of DSC data shows 86% solids 
at 50.degree. F. 13% solids at 70.degree. F., and 0% solids at 80.degree. 
F. 
Example 17 
In this example, a blend of predominantly LSL/LLS propionyl-stearoyl 
glyceride and butyryl-stearoyl glyceride (depicted in Examples 10 and 14 
above) is prepared. 
A propionyl-stearoyl glyceride component is prepared by reacting a 1:1 
molar ratio of distearin with propionic anhydride. A 2-L, 2-neck flask 
equipped with a thermometer, reflux condenser, heating mantle and stirrer 
is charged with 367 g distearin, which is melted prior to adding 76 g 
propionic anhydride. The mixture is refluxed at 125.degree. C. for 
.about.5 hours, left to stand overnight at room temperature, and refluxed 
with stirring at 80.degree. C. for 6 hours. The mixture is distilled to 
yield a solid crude product that is dissolved in hexane and washed with 
water until neutral. Hexane is removed in vacuuo and the off-white product 
solid, dried. The yield is 374 g (93%). 
A butyryl-stearoyl glyceride component is prepared by reacting distearin 
with butyric anhydride (.about.99% pure, obtained from Aldrich). A 3-L, 
3-neck flask equipped with a thermometer, reflux condenser, heating mantle 
and stirrer is charged with 720 g distearin, which is half melted prior to 
adding 204 mL butyric anhydride. The mixture is heated for .about.21/2 
hours at 85.degree. C., left to stand without heat for two days, and 
refluxed at 85.degree. C. for 8 hours. The mixture is distilled twice at 1 
mm Hg to yield 743 g (93%) of a hard, light brown solid. 
The butyryl-stearoyl glyceride component (650 g) is mixed with the 
propionyl-stearoyl glyceride component (350 g) in a 2-L beaker and heated. 
The blend is steam deodorized at 180.degree. C., 1 mm Hg, 30 mL H.sub.2 O 
to yield a product having a melting point of 37.degree. to 39.degree. C. 
and an NMR S/L ratio of 0.6. 
Example 18 
In this example, another blend of propionyl-stearoyl glyceride and 
butyryl-stearoyl glyceride similar to the one prepared in Example 17 
above, but having a different array of components, is prepared. 
A propionyl-stearoyl glyceride component is prepared by reacting distearin 
with propionic anhydride. A 3-L, 3-neck flask equipped with a stirrer, 
heating mantle, thermometer, and reflux condenser is charged with 500 g of 
a distearin prepared as set out in Example 13, except that no 
2-amino-propanol and no recrystallization steps are made. NMR analysis 
indicates the starting material comprises 90% distearin, 8% tristearain, 
and 2% monostearin. This is melted prior to adding 111 g propionic 
anhydride (Aldrich). The mixture is refluxed 14 hours, distilled, and 
purified in a falling-film still (&lt;1 mm Hg, 180.degree. C.). The final 
product, 545 g (95% yield), is a dark brown solid having a melting point 
of 58.degree. to 60.degree. C. 
A butyryl-stearoyl glyceride component is prepared by reacting distearin 
with butyric anhydride. A 2-L, 3-neck flask equipped with a stirrer, 
heating mantle, thermometer, and reflux condenser is charged with 562 g of 
the distearin employed in the propionyl-stearin synthesis outlined above. 
This is melted prior to adding 150 g butyric anhydride (Aldrich). The 
mixture is refluxed at reduced pressure 2 hours, distilled, and purified 
in a falling-film still (&lt;1 mm Hg, 180.degree. C.). The final product, 605 
g (96% yield), is a dark brown solid which NMR analysis shows to have a 
triglyceride content of 96%. 
The propionyl-stearcyi glyceride component (387 g) is melted with the 
butyryl-stearoyl glyceride component (721 g) and stirred well. The blend 
is purified using a steam deodorizer at 0.6 mm Hg, 175.degree. C., 35 mL 
water to yield a product comprising 29% propionyl-stearoyl glyceride and 
61% butyryl-stearoyl glyceride having an NMR S/L ratio of 0.8. 
Example 19 
In this example, a blend of predominantly SSL and SLS diacetyl-stearoyl 
glyceride and dipropionyl-stearoyl glyceride components (depicted in 
Examples 3 and 5 above) is prepared. 
An diacetyl-stearoyl glyceride component is prepared by reacting 
monostearin with acetic anhydride. A 2-L, 3-neck flask equipped with a 
stirrer, heating mantle, thermometer,and reflux condenser is charged with 
406 g monostearin obtained from Spectrum Chemicals. This is melted prior 
to addition of acetic anhydride (Aldrich), and the mixture is refluxed at 
140.degree. C. for 2 hours, held overnight without heat, and refluxed for 
3 more hours. Acetic acid is distilled off, and the product purified in a 
falling-film still (1 mm Hg, 180.degree. C.) to yield 438 g (83%) of a 
golden yellow solid, which NMR show to contain triglycerides only. 
A dipropionyl-stearoyl glyceride component is prepared by reacting 
monostearin with propionic anhydride. A 3-L, 3-neck flask equipped with a 
stirrer, heating mantle, thermometer, and reflux condenser is charged with 
771 g monostearin obtained from Spectrum Chemicals. This is melted and 552 
g propionic anhydride (Aldrich) is added. The mixture is refluxed 3.5 
hours, held overnight without heating, and refluxed 5 more hours. The 
product is distilled and purified in a falling-film still (&lt;1 mm Hg) to 
yield 935 g (94%) of a clear, golden yellow liquid. 
The diacetyl-stearoyl glyceride component (421 g) and the 
dipropionyl-stearoyl glyceride component (780) are melted together, mixed 
well, and steam deodorized at 0.6 mm Hg, 168.degree. C., 40 mL H.sub.2 O. 
The final blend comprises 31% diacetyl-stearin and 69% 
dipropionyl-stearin, and has an NMR S/L ratio of 1.8. 
Example 20 
In this example, reduced calorie fat mixtures are prepared by 
interesterifying hydrogenated canola (refined, low erucic rapeseed oil 
containing 4% palmitic acid, hydrogenated at 180.degree. C. and 60 lbs 
hydrogen until the Iodine Value (IV) is .ltoreq.3) with tributyrin 
(obtained commercially from Eastman Kodak). A Mettler dropping point 
(M.D.P.) is determined for each mixture using a Mettler Thermosystem FP 
800 following A.O.C.S. Method Cc 18-80 (1989). A solid fat index (S.F.I.) 
is obtained using A.O.C.S. Method Cd 10-57 (1989). Each mixture is 
subjected to proton nuclear magnetic resonance (NMR) spectroscopy; 
integration of the intensities of the various groups gives an estimate of 
the molar ratio of short (in this case, butyric) to long acids (S/L) 
present. 
One molar equivalent hydrogenated canola (899 g) and 2 to 4.5 molar 
equivalents tributyrin are interesterified in the presence of 0.2 to 0.3% 
sodium methoxide by heating to .about.110.degree. C. with agitation under 
a vacuum for about half an hour until color develops. (The M.D.P. may be 
checked at this time, and the reaction continued if the M.D.P. has not 
dropped sufficiently.) Phosphoric acid (.about.0.2 to .about.0.5%, at 
least twice the amount of sodium methoxide) is added to stop each reaction 
and neutralize the mixture, followed by the addition of 0.5% activated 
bleaching clay (Tonsil Optimum FF), 0.5% diatomaceous earth, and 1000 ppm 
citric acid (dissolved in water) to decolorize and remove soaps. The 
treatment is continued for 1/2 to 1 hour at 110.degree. C. The products 
are cooled to 80.degree. C., filtered, bleached, and steam deodorized at 
210.degree. C. for 2 to 3 hours. 
Using this procedure, a 1:25 molar reactant ratio of hydrogenated canola to 
tributyrin yields a liquid product having a M.D.P. of 18.6.degree. C. and 
an NMR S/L of 2.0. Conversely, a 1:0.5 molar ratio yields a waxy product 
having a M.D.P. of 63.0.degree. C. and an NMR S/L of 0.5; similarly, a 1:1 
molar ratio of hydrogenated canola to tributyrin yields a product having a 
M.D.P. of 57.9.degree. C. and an NMR S/L of 0.8. Using intermediate 
reactant ratios, the following triglyceride mixtures are obtained: 
______________________________________ 
Hydrogenated Canola:Tributyrin Reactant Molar Ratio 
1:2 1:2.5 1:3 1:3.5 
1:4 1:4.5 
1:12 
______________________________________ 
M.D.P., 
.degree.C. 
35.1 31.8 30.4 28.7 27.5 26.6 22.1 
S.F.I. 50.degree. F. 
68.8 69.5 66.8 63.6 63.8 63.4 54.3 
70.degree. F. 
52.3 53.6 39.6 33.1 29.8 24.7 3.8 
80.degree. F. 
24.0 23.7 8.8 4.7 3.9 2.1 0.0 
92.degree. F. 
10.0 9.2 4.3 3.2 2.3 1.6 0.0 
100.degree. F. 
9.2 8.8 4.0 2.6 0.0 0.0 
NMR 1.2 1.2 1.3 1.4 1.5 1.4 1.8 
S/L 
______________________________________ 
Example 21 
This example illustrates a method of analyzing hydrogenated 
canola/tributyrin triglyceride mixtures prepared in Example 20 using 
supercritical fluid chromatography (S.F.C.) to separate and quantify the 
mixture components. 
After filtering through a 0.45 micron filter, 0.1 ul of a 30 to 50 mg/ml 
sample is injected onto a 1.times.100 mm Deltabond Cyano.TM. column from 
Keystone Scientific in a Suprex Model 200A S.F.C. having an S.F.C.- grade 
carbon dioxide mobile phase and an oven temperature of 125.degree. C. A 
linear pressure gradient of 100 to 300 atmospheres is applied over a 
course of 20 minutes (i.e., 10 atm/min), followed by a hold at 300 
atmospheres for 10 minutes. A flame ionization detector at 400.degree. C. 
detects emerging mixture components run against an internal standard of 
methyl tetradecanoate (10 to 12 mg/mL) in methylene chloride. External 
standards of mono, di, and tristearin (.about.10 mg/mL each) are run under 
identical conditions. Using these peak areas, the peak areas of the sample 
are normalized, added together, and divided by the total to obtain the 
following percentages of LSS & SLS, LLS & LSL, and LLL in the mixtures: 
______________________________________ 
Hydrogenated Canola:Tributyrin Reactant Molar Ratio 
1:0.5 
1:1 1.2 1:2.5 
1:3 1:3.5 
1.4 1:4. 
______________________________________ 
% LSS/SLS 
17.0 39.2 57.2 67.2 69.4 73.2 78.1 80.2 
% LLS/LSL 
38.5 43.8 34.7 28.8 27.1 24.0 20.5 18.4 
% LLL 44.5 17.1 8.1 4.0 3.4 2.7 1.4 1.4 
______________________________________ 
The mixtures prepared in Example 20 thus include, after purification, 
compounds of the formula 
##STR22## 
where R' is --(CO)--(CH.sub.2).sub.2 CH.sub.3 and 
R is derived from hydrogenated canola oil 
Example 22 
In this example, reduced calorie fat mixtures are prepared by 
interesterifying one mole hydrogenated canola (obtained as described in 
Example 20) with 2.5, 3.5, or 12 moles tripromionin (obtained commercially 
from Pfaltz & Bauer). 
Using the preparative and analytical procedures outlined in Example 20, the 
following M.D.P., S.F.I., and NMR S/L data cn the products are obtained: 
______________________________________ 
Hydrogenated Canola:Tripropionin Reactant Molar Ratio 
1:2.5 1:3.5 1:12 
______________________________________ 
M.D.P., .degree.C. 
34.4 33.5 27.2 
S.F.I. 50.degree. F. 
70.6 61.7 54.9 
70.degree. F. 
66.1 56.5 32.2 
80.degree. F. 
51.2 35.5 0.8 
92.degree. F. 
7.3 0.0 0.0 
100.degree. F. 
4.3 0.0 0.0 
NMR S/L 1.2 1.4 2.2 
______________________________________ 
Example 23 
Reduced calorie fat mixtures are prepared as described in Example 22, 
except that the interesterification mixture contains hydrogenated canola 
(obtained as described in Example 20) with both tripropionin (1.25, 1.75, 
and 6 moles to 1 mole hydrogenated canola) and tributyrin (in the same 
proportions). 
Using the preparative and analytical procedures outlined in Example 22, the 
following M.D.P., S.F.I., and NMR S/L data on the products are obtained: 
______________________________________ 
Hydrogenated Canola:Tributyrin:Tripropionin Reactant 
Molar Ratio 
1:1.25:1.25 
1:1.75:1.75 
1:6:6 
______________________________________ 
M.D.P., .degree.C. 
32.5 30.0 24.4 
S.F.I. 50.degree. F. 
67.7 65.0 51.7 
70.degree. F. 
54.0 44.6 13.8 
80.degree. F. 
28.1 16.6 0.0 
92.degree. F. 
4.7 1.4 0.0 
100.degree. F. 
4.4 2.3 0.0 
NMR S/L 1.3 1.5 2.1 
______________________________________ 
Example 24 
Reduced calorie fat mixtures are prepared as described in Examples 20 and 
23, except that the interesterification mixture contains hydrogenated 
canola with both tripropionin (1.25 moles, 2.25 moles and 6 moles per mole 
hydrogenated canola) and triacetin (in the same proportions), the reaction 
temperature is 120.degree. to 125.degree. C., and 0.5% sodium methoxide is 
employed. 
Using the preparative and analytical procedures outlined in Example 22, the 
following M.D.P. and S.F.I. data on the products are obtained: 
______________________________________ 
Hydrogenated Canola:Tripropionin:Triacetin Reactant 
Molar Ratio 
1:1.25:1.25 
1:2.25:2.25 
1:6:6 
______________________________________ 
M.D.P., .degree.C. 
36.8 33.8 31.4 
S.F.I. 50.degree. F. 
71.4 69.8 54.8 
70.degree. F. 
69.8 56.0 34.2 
80.degree. F. 
64.3 1.5 0.0 
92.degree. F. 
23.0 0.0 0.0 
100.degree. F. 
0.2 0.0 0.0 
NMR S/L 1.3 1.6 2.1 
______________________________________ 
Example 25 
Reduced calorie fat mixtures are prepared as described in Examples 20 and 
23, except that the interesterification mixture contains hydrogenated 
canola (denoted below as "H-Canola") with triacetin, tripropionin, and 
tributyrin (in proportions set out below). 
Using the preparative and analytical procedures outlined in Example 22, the 
following M.D.P. and S.F.I. data on the products are obtained: 
______________________________________ 
H-Canola:Triacetin:Tripropionin:Tributyrin Molar Reactant Ratio 
1:0.5:1.0:1.0 
1:0.7:1.4:1.4 
1:2:4:4.8:4.8 
______________________________________ 
M.D.P., .degree.C. 
35.0 31.3 26.8 
S.F.I. 50.degree. F. 
68.6 67.8 63.3 
70.degree. F. 
63.2 56.5 36.1 
80.degree. F. 
42.5 29.6 1.0 
92.degree. F. 
4.6 0.0 0.0 
100.degree. F. 
4.6 0.0 0.0 
NMR S/L 1.4 1.6 2.1 
______________________________________ 
Example 26 
This example illustrates how the triglyceride mixtures of this invention 
are screened for caloric availability by a carefully controlled in vivo 
animal feeding study. 
An experimental relationship between oil calories ingested and animal body 
weight gain is established by monitoring the body weight gain associated 
with consumption of a nutritionally balanced diet containing varying 
concentrations of a reference substance such as corn oil which has a known 
caloric availability. Correlations between total calories ingested and 
body weight gain are excellent (r=0.99). 
Caloric availability of an unknown substance is evaluated by substituting a 
specific weight of the unknown substance for the reference substance and 
observing the body weight gain. The gain in body weight is equated to a 
total number of calories using the correlation previously established for 
the reference data. The estimated number of calories ingested are divided 
by the weight of unknown substance to give the apparent calories 
metabolized per gram for the unknown substance. 
The test animals are weakling male Sprague-Dawley rats, weighing 
approximately 50 to 60 g prior to acclimation. After acclimation for 3 to 
10 days, the test duration is 14 days. The dietary requirements are 
established by observing the actual feed consumption of animals provided 
with unlimited feed. All diets are prepared to contain 50% of the 
established dietary requirements plus any supplements of reference or 
unknown substances. In all tests so designed the test animals are 
maintained in very good health. 
The animals are housed singly in suspended wire mesh cages which conform to 
the size recommendatins in the Guide for the Care and Use of Laboratory 
Animals, Department of Health, Education and Welfare, National Institute 
of Health Bulletin No. 78.23. Litter paper is changed at least three times 
a week. The animal room is temperature controlled, with a 12-hour 
light/dark cycle, and kept clean and vermin free. Water is provided 
ad-libitum. 
There are ten animals per group. The test feeds are NIH 07 Open Formula 
Rodent Chow diets manufactured by Zeigler Bros., obtained as pellets or 
meal. Fortified diets employ 0.2% AIN-76A vitamin pre-mix obtained from 
Teklad. Weight gains are measured at days 0, 3, 7, 10, and 14. 
The test groups are as follows: 
______________________________________ 
Group Test Diet Feeding Regimen 
______________________________________ 
1 NIH-07 Ad-libitum 
2 NIH-07 Pair Fed 50% of Gp. 1 
3 As Gp. 2 + 7% corn oil 
Pair Fed 50% of Gp. 1 
4 As Gp. 2 + 14% corn oil 
Pair Fed 50% of Gp. 1 
5 As Gp. 2 + 21% corn oil 
Pair Fed 50% of Gp. 1 
______________________________________ 
Rats were fed a diet of 21% triglyceride test substances prepared as 
described in the above Examples as test compounds under the foregoing 
procedure, and their weight gains were determined. Based upon the base 
line corn oil control data, and the data from the test substances, the 
following caloric availability data (expressed as kcal/gram) were 
determined: 
______________________________________ 
Low Calorie Triglycerides kcal/g 
______________________________________ 
Example 9 Acetyl-stearoyl Glycerides (S/L = 0.9) 
3.9 
Example 10 Propionyl-stearoyl Glycerides (S/L = 0.9) 
3.9 
Example 11 Propionyl-stearoyl Glycerides (S/L = 1.3) 
4.4 
Example 12 Propionyl-stearoyl Glycerides (S/L = 2.0) 
4.1 
Example 14 Butyryl-stearoyl Glycerides (S/L = 0.9) 
4.0 
Example 15 Butyryl-stearoyl Glycerides (S/L = 1.2) 
4.4 
Example 16 Butyryl-stearoyl Glycerides (S/L = 1.9) 
4.2 
Examnle 17 Butyryl/propionyl-stearoyl Glycerides 
3.1 
Example 18 Butyryl/propionyl-stearoyl Glycerides 
1.7 
Example 19 Acetyl/propionyl-stearoyl Glycerides 
4.8 
Example 20 1:1 Hydrogenated Canola/Tributyrin 
3.6 
Example 20 1:2 Hydrogenated Canola/Tributyrin 
3.9 
Example 20 1:2.5 Hydrogenated Canola/Tributyrin 
3.9 
Example 20 1:3 Hydrogenated Canola/Tributyrin 
3.8 
Example 20 1:3.5 Hydrogenated Canola/Tributyrin 
3.8 
______________________________________ 
Example 27 
This example describes feeding studies using the method described in 
Example 26 above, except that rats were fed a diet of 21%, 15%, 10% and 5% 
triglyceride test substance. The test substance is a triglyceride mixture 
obtained by the interesterification of hydrogenated canola and tributytin 
in a 1:2.5 molar ratio as described in Example 20. 
Caloric availability is estimated by comparing weight gain of rapidly 
growing male rats fed corn oil compared to weight gain of rats fed the 
test oil. 
To conduct the experiment, a group of 10 rats are fed NIH-07 open formula 
died ad libitum. This group is started on the diet one day ahead of all 
the others. Each day the feed consumption for the ad libitum group is 
determined. 
All experimental groups receive 50% of the NIH-07 diet consumed on the 
previous day. The standard curve for growth is developed by supplementing 
the NIH-07 diets with various levels of corn oil (0, 5, 10, 15 and 21%). 
The mean body weight gain for each corn oil supplemented sample is 
regressed against the calories from corn oil (feed consumption * % corn 
oil * 9) for 0, 5, 10, and 15% corn oil to establish the equation of the 
standard curve. The 21% corn oil weight gain is dropped from the standard 
curve calculation because the response is not linear at that level (the 
animals being saturated with amount of fat in the diet). The weight gain 
for rats consuming test oil are compared to the standard curve, and 
calories are calculated using the formula: 
##EQU1## 
The following caloric availability are obtained: 
______________________________________ 
Dietary Level kcal/g 
______________________________________ 
5% 4.6.sup.a 
10% 6.0.sup.b 
15% 5.8.sup.a 
21% 4.6%.sup.c 
______________________________________ 
Example 28 
In this example, reduced calorie fat mixtures are prepared using the 
protocol described in Example 20 by interesterifying hydrogenated canola 
and tributyrin. With a 1:12 molar reactant ratio of hydrogenated canola to 
tributyrin, a product with an M.D.P. of 22.5.degree. C. and an NMR S/L 
ratio of 1.8 was obtained; the S.F.I. is 50.7% at 50.degree. F., 3.9% at 
70.degree. F., and 0% at 80%. Increasing the proportion of tributyrin to 
1:25 yielded a product with an M.D.P. of 18.6.degree. C. and an NMR S/L 
ratio of 2.0; the S.F.I. is 1.7% at 50.degree. F., 2.6% at 70.degree. F., 
and 0% at 80.degree. F. 
Example 29 
In this example, reduced calorie fat mixtures are prepared using the 
protocol described in Example 20 by interesterifying one mole fully 
hydrogenated high erucic rapeseed oil (obtained from CSP) with 2.5, 4.0, 
or 12 moles tripropionin (obtained commercially from Pfaltz & Bauer). 
Using the preparative and analytical procedures outlined in Example 20, 
the following M.D.P., S.F.I., and NMR S/L data on the products are 
obtained: 
______________________________________ 
Hydrogenated Rapeseed:Tripropionin Reactant Molar Ratio 
1:2.5 1:4 1:12 
______________________________________ 
M.D.P., .degree.C. 
44.6 42.5 39.2 
S.F.I. 50.degree. F. 
79.3 76.7 68.7 
70.degree. F. 
74.9 72.0 61.8 
80.degree. F. 
73.6 68.9 52.8 
92.degree. F. 
60.4 48.7 24.9 
100.degree. F. 
38.7 25.0 3.5 
NMR S/L 1.2 1.5 1.9 
______________________________________ 
Example 30 
In this example, reduced calorie fat mixtures are prepared using the 
protocol described in Example 20 by interesterifying one mole fully 
hydrogenated menhaden fish oil (obtained from Zapata Hayne) with 2.5, 4.0, 
or 12 moles tripropionin (obtained commercially from Pfaltz & Bauer). 
Using the preparative and analytical procedures outlined in Example 20, the 
following M.D.P., S.F.I., and NMR S/L data on the products are obtained: 
______________________________________ 
Hydrogenated Fish Oil:Tripropionin Reactant Molar Ratio 
1:2.5 1:4 1:12 
______________________________________ 
M.D.P., .degree.C. 
32.7 31.3 25.9 
S.F.I. 50.degree. F. 
60.5 55 40.6 
70.degree. F. 
41.3 32.4 13.3 
80.degree. F. 
22.2 12.3 0.2 
92.degree. F. 
3.0 0.0 0.0 
100.degree. F. 
0.3 0.0 0.0 
NMR S/L 1.1 1.4 2.0 
______________________________________ 
Example 31 
Using the procedure outlined in Example 20, tributyrin is interesterified 
with safflower oil obtained from Welch, Holme, and Clark. A liquid oil 
(having no solids at 50.degree. F. to 100.degree. F.) is obtained with oil 
to tributyrin reactant molar ratios of 1:2.5, 1:4, and 1:12. 
Example 32 
Using the procedure outlined in Example 20, tripropionin is interesterified 
with safflower oil. A liquid oil (having no solids at 50.degree. to 
100.degree. F.) is obtained with oil to tributyrin reactant molar ratios 
of 1:2.5, 1:4, and 1:12. 
Example 33 
In this example, reduced calorie fat mixtures are prepared using the 
protocol described in Example 20 by interesterifying hydrogenated canola 
oil with tripropionin and safflower oil. 
With a safflower:hydrogenated canola:tripropionin reactant molar ratio of 
0.66:0.33:12, and oil with no solids at 50.degree. to 100.degree. F. is 
obtained. Using the preparative and analytical procedures outlined in 
Example 20, the following S.F.I. data on products prepared using other 
ratios are obtained: 
______________________________________ 
Safflower:Hydrogenated Canola:Tripropionin Reactant 
Molar Ratio 
S.F.I. 0.33:0.66:2.5 
0.33:0.66:12 
0.66:0.33:2.5 
______________________________________ 
50.degree. F. 
24.1 16.0 1.5 
70.degree. F. 
4.7 0.2 0 
80.degree. F. 
1.2 0 
92.degree. F. 
0.6 
100.degree. F. 
0 
______________________________________ 
Example 34 
Using the feeding study protocol set out in Example 26, rats were fed a 
diet of 21% triglyceride test substances prepared as described in the 
previous Examples as test compounds. As used herein, hydrogenated canola 
is abbreviated "H-Canola." Based upon the base line corn oil control data, 
and the data from the test substances, the following caloric availability 
data (expressed as kcal/gram) were calculated as described in Example 27: 
______________________________________ 
kcal/ 
Low Calorie Triglycerides g 
______________________________________ 
Ex. 22 Hydrogenated Canola/Tripropionin (S/L = 1.2) 
4.7 
Ex. 22 Hydrogenated Canola/Tripropionin (S/L = 1.3) 
4.3 
Ex. 22 Hydrogenated Canola/Tripropionin (S/L = 2.2) 
4.7 
Ex. 23 H-Canola/Tripropionin/Tributyrin (S/L = 1.3) 
4.8 
Ex. 23 H-Canola/Tripropionin/Tributyrin (S/L = 1.3) 
4.8 
Ex. 23 H-Canola/Tripropionin/Tributyrin (S/L = 2.1) 
5.6 
Ex. 24 H-Canola/Triacetin/Tripropionin (S/L = 1.3) 
5.0 
Ex. 24 H-Canola/Triacetin/Tripropionin (S/L = 1.6) 
5.0 
Ex. 24 H-Canola/Triacetin/Tripropionin (S/L = 2.1) 
5.4 
Ex. 25 S/L 1.4 5.2 
H-Canola/Triacetin/Tripropionin/Tributyrin 
Ex. 25 S/L 1.6 5.3 
H-Canola/Triacetin/Tripropionin/Tributyrin 
Ex. 25 S/L 2.1 5.7 
H-Canola/Triacetin/Tripropionin/Tributyrin 
Ex. 28 1:12 Hydrogenated Canola/Tributyrin (S/L = 1.8) 
5.2 
Ex. 28 1:25 Hydrogenated Canola/Tributyrin (S/L = 2.0) 
6.2 
Ex. 31 Safflower/Tributyrin (S/L = 0.9) 
6.7 
Ex. 31 Safflower/Tributyrin (S/L = 1.1) 
6.6 
Ex. 31 Safflower/Tributyrin (S/L = 1.5) 
6.7 
Ex. 32 Safflower/Tripropionin (S/L = 1.2) 
6.9 
Ex. 32 Safflower/Tripropionin (S/L = 1.3) 
6.5 
Ex. 32 Safflower/Tripropionin (S/L = 2.0) 
6.0 
______________________________________ 
Example 35 
Using the feeding study protocol set cut in Example 26, rats were fed a 
diet of 10% triglyceride test substances prepared as described in the 
above Examples as test compounds. As used herein, hydrogenated canola is 
abbreviated "H-Canola" and hydrogenated high erucic rapeseed is 
abbreviated "H-Rapeseed." Based upon the base line corn oil control data, 
and the data from the test substances, the following caloric availability 
data (expressed as kcal/gram) were calculated as described in Example 27: 
______________________________________ 
kcal/ 
Low Calorie Triglycerides g 
______________________________________ 
Example 20 1:2.5 H-Canola/Tributyrin and Triacetin 
3.3 
Example 20 1:2.5 H-Canola/Tributyrin and Triacetin 
3.9 
Example 29 H-Rapeseed/Tripropionin (S/L 1.2) 
3.8 
Example 29 H-Rapeseed/Tripropionin (S/L 1.5) 
4.1 
Example 29 H-Rapeseed/Tripropionin (S/L 1.9) 
5.7 
Example 30 Hydrogenated Fish Oil/Tripropionin (S/L 1.2) 
7.0 
Example 30 Hydrogenated Fish Oil/Tripropionin (S/L 1.4) 
7.4 
Example 30 Hydrogenated Fish Oil/Tripropionin (S/L 2.0) 
6.6 
Example 33 H-Canola/Safflower/Tripropionin (S/L 1.2) 
6.8 
Example 33 H-Canola/Safflower/Tripropionin (S/L 1.5) 
6.3 
Example 33 H-Canola/Safflower/Tripropionin (S/L 1.9) 
7.0 
Example 33 H-Canola/Safflower/Tripropionin (S/L 2.0) 
7.3 
______________________________________ 
Example 36 
Reduced calorie fat mixtures are prepared as described in Example 24, 
except that the interesterification mixture contains different proportions 
of hydrogenated canola (abbreviated "H-Canola"), tripropionin and 
triacetin. Using the preparative and analytical procedures outlined in 
Example 22, the following M.D.P. and S.F.I. data on the products are 
obtained: 
______________________________________ 
H-Canola:Tripropionin:Triacetin Reactant Molar Ratio 
1:1:11 
1:11:1 
______________________________________ 
M.D.P., .degree.C. 35.0 17.6 
S.F.I. 50.degree. F. 64.4 55.0 
70.degree. F. 62.4 32.3 
80.degree. F. 58.7 7.4 
92.degree. F. 28.5 0.0 
100.degree. F. 
0.4 0.0 
NMR S/L 1.8 1.8 
______________________________________ 
Example 37 
This example details the physical and chemical characterization of several 
reduced calorie triglyceride mixtures of this invention. Mixture A is 
prepared by the interesterification of 2.5 moles tributyrin with 1 mole 
hydrogenated canola as outlined in Example 20. The M.D.P. determined using 
A.O.C.S. Method Cc 18-80 is 30.9.degree. C. and the S.F.I. obtained using 
A.O.C.S. Method Cd 10-57 shows 64.8% solids at 50.degree. F., 38.7% at 
70.degree. F., 11.4% at 80.degree. F., 4.9% at 92.degree. F., and 5.2% at 
100.degree. F. Mixture B is prepared by the interesterification of 11 
moles of triacetin and 1 mole tripropionin with 1 mole of hydrogenated 
canola, and mixture C is prepared by the interesterification of 1 mole of 
triacetin and 11 moles of tripropionin with 1 mole of hydrogenated canola 
as described in Example 36. 
Viscosity is determined using a Haake viscometer, Rotovisco.TM. model RV12, 
with a M-500 measuring head consisting of a sensor system cup and a bell 
shaped rotor that are manually attached to a temperature vessel, then 
connected to a circulator and a temperature controlled waterbath. The 
method measures simple shear at two temperatures in the annular gap 
between two concentric cylinders. Continuous measurements of torque at 
zero up to 100 rpm are recorded on a chart from which viscosity of the 
liquid fat is calculated. 
In the practice of viscosity determinations, the sample is melted (if not 
already liquid) and stirred thoroughly; the temperature during melting 
does not exceed the melting point of the sample by more than 10.degree. C. 
For each temperature, the measured value (S) from the chart is read at the 
point that intercepts the curve at 50 rpm and the viscosity calculated 
using the following equation: 
##EQU2## 
where G is a constant instrument factor dependent on the torque of the 
measuring drive unit and the geometry of the sensor system (329 with the 
4.0 Sensor System NV and the equipment described herein); 
S is the measured value in scale units (from the chart); and 
n is the test speed in rpm at the measured value. 
Fatty acids are determined using proton NMR as described heretofore, with 
results denoted in Table I following using the abbreviation "but." for 
butyric acid, "ac." for acetic acid, "pro." for propionic acid, and "st." 
for stearic acid. Short/long chain ratios are also determined using proton 
NMR, and the heats of fusion are determined using DSC as described 
heretofore. The other measurements follow A.O.C.S. methods as listed; 
Lovibond Color is assayed using a 1 inch column. 
Using these analytical techniques the following data are obtained: 
TABLE I 
__________________________________________________________________________ 
Reduced Calorie Triglyceride Mixture 
Properties Method A B C 
__________________________________________________________________________ 
Fatty acids 
Proton 51% ac. 
7% ac. 
(mole %) NMR 54% but. 
13% pro. 
57% pro. 
46% st. 
36% st. 
36% st. 
Short/Long Proton 1.2 1.8 1.8 
Chain Ratio 
NMR 
Mettler AOCS Method 
87.6.degree. F. 
95.0.degree. F. 
63.7.degree. F. 
Drop Point Cc 18-80 
Smoke Point 
AOCS Method 
310.degree. F. 
260.degree. F. 
275.degree. F. 
Cc 9a-48 
Flash Point 
AOCS Method 
480.degree. F. 
470.degree. F. 
470.degree. F. 
Cc 9a-48 
Fire Point AOCS Method 
510.degree. F. 
495.degree. F. 
495.degree. F. 
Cc 9a-48 
Peroxide Value 
AOCS Method 
0.20 0.45 0.77 
Cd 8-53 meq/kg 
meq/kg meq/kg 
Free Fatty Acids 
AOCS Method 
0.23% 0.78% 0.45% 
Ca 5a-40 
Congeal Point 
AOCS Method 
30.6.degree. C. 
33.8.degree. C. 
27.7.degree. C. 
Cc 14-59 
Sp. Gravity @ 60.degree. C. 
AOCS Method 
0.9097 
0.9337 0.9347 
Cc 10-25 
Refract Index 
AOCS Method 
1.4396 
1.4385 1.4398 
@ 60.degree. C. 
Cc 7-25 
Saponification 
AOCS Method 
287 347 337 
Value Cd 3-25 
AOM Oxidative 
AOCS Method 
295.sup.+ hrs 
290.sup.+ hrs 
290.sup.+ hrs 
Stability Cd 12-57 
Solid Fat AOCS Method 
78.2% 82.1% 68.1% 
Content @ 50.degree. F. 
Cd 16-81 
Solid Fat AOCS Method 
49.3% 78.4% 43.0% 
Content @ 70.degree. F. 
Cd 16-81 
Solid Fat AOCS Method 
11.8% 71.7% 5.1% 
Content @ 80.degree. F. 
Cd 16-81 
Solid Fat AOCS Method 
7.3% 29.9% 3.8% 
Content @ 92.degree. F. 
Cd 16-81 
Solid Fat AOCS Method 
7.8% 4.9% 4.7% 
Content @ 100.degree. F. 
Cd 16-81 
Viscosity @ 100.degree. F. 
Haake 32.9 cps 
35.1 cps 
32.9 cps 
Viscometer 
Viscosity @ 150.degree. F. 
Haake 26.3 cps 
19.7 cps 
19.7 cps 
Viscometer 
Lovibond Color 
AOCS Method 
8 Red/ 
20 Red/ 
16 Red/ 
Cc 13b-45 
79 Yellow 
77 Yellow 
70 Yellow 
Heat of Fusion 
DSC 121.6 99.4 86.9 
mJ/mg mJ/mg mJ/mg 
__________________________________________________________________________ 
Example 38 
This example compares the melting point behavior of monostearin derivatives 
as a function of chain length. Each derivative bears one stearic acid 
residue per molecule and two identical short or medium chain substituents. 
Diacetyl monostearin is prepared by melting 968.22 g (2.7 moles) 
1-glycerol-rac-monostearin obtained from Spectrum Chemicals (Lot # FC026) 
in a reaction flask equipped with a magnetic stirrer, heating mantle, 
thermometer, and reflux condenser prior to adding 578.85 g (5.67 moles) 
acetic anhydride (Aldrich Chemicals). The reaction flask is heated to 
140.degree. C. for 5 hours at atmospheric pressure, and the acetic acid 
side product is removed by vacuum distillation at 90 mm Hg, 95.degree. C. 
The yield of distillate is quantitative. The dark brown waxy product is 
decolorized with activated charcoal and heptane for 10 hours; the carbon, 
removed with hot vacuum filtration; and heptane, removed by vacuum, 
yielding a golden yellow waxy product which is passed through a falling 
film still equipped with mesitylene as the boiling solvent (168.degree. 
C., &lt;1 mm Hg) and deodorized. The yield is 2.52 moles (92.9%) of a golden 
yellow wax having a capillary melting point of 35.degree.-36.degree. C. 
and a DSC melting point of 35. NMR in CDCl.sub.3 (chemical shifts in ppm): 
5.25 (m, 1H), 4.3 (dd, 2H), 4.15 (dd, 2H), 2.3 (m, 2H), 2.1 (m, 6H), 1.6 
(m, 2H), 1.3 (m, 28H), 0.9 (t, 3H). 
Dipropionyl monostearin is prepared by melting 771 g (2.15 moles) 
1-glycerol-rac-monostearin obtained from Spectrum Chemicals (Lot # FC026) 
in a 2-L reaction flask equipped with a magnetic stirrer, heating mantle, 
thermometer, and reflux condenser prior to adding 552 g (4.24 moles) 
propionic anhydride (Aldrich Chemicals). The reaction flask is heated to 
167.degree. C. for 8 hours at atmospheric pressure, and the side product 
removed by vacuum distillation at 65 mm Hg, 35.degree. C. The golden 
yellow solf solid product is passed through a falling film still equipped 
with mesitylene as a boiling solvent (168.degree. C., &lt;1 mm Hg) and 
deodorized to afford 935.5 g (1.98 moles, 94%) of a golden yellow soft 
solid having a DSC melting point of 24.degree. C. SFC analysis: 96.5% 
SPP/PSP, 3.3% SPS/SSP, 0.2% SSS, &lt;&lt;1% unreacted material. NMR in 
CDCl.sub.3 (chemical shifts in ppm): 5.25 (m, 1H), 4.3 (dd, 2H), 4.15 (dd, 
2H), 2.35 (m, 6H), 1.6 (m, 2H), 1.25 (m, 28H), 1.1 (m, 6H), 0.9 (t, 3H). 
Dibutyryl monostearin is prepared by melting 864.2 g (2.47 moles) 
1-glycerol-rac-monostearin obtained from Spectrum Chemicals (Lot # FC026) 
in a 2-L reaction flask equipped with a magnetic stirrer, heating mantle, 
thermometer, and reflux condenser prior to adding 770.4 g (4.87 moles) 
burytic anhydride (Aldrich Chemicals). The reaction flask is heated to 
180.degree. C. for 16 hours at atmospheric pressure, and the butyric acid 
side product is removed by vacuum distillation at 100 mm Hg, 105.degree. 
C. The yield of distillate is quantitative. The milky golden liquid 
product is passed through a falling film still equipped with mesitylne as 
the boiling solvent (168.degree. C., &lt;1 mm Hg) and steam deodorized at 
210.degree. C., &lt;1 mm Hg. The yield is 2.08 moles (86.8%) of a golden 
yellow very soft solid having a DSC melting point of 21.degree. C. SFC 
analysis: 94.2% SBB/BSB, 5.3% SBB/BSB, 4% 1-monostearin. NMR in CDCl.sub.3 
(chemical shifts in ppm) indicates 95% product: 5.25 (m, 1H), 4.3 (dd, 
2H), 4.15 (dd, 2H), 2.35 (m, 6H), 1.6 (m, 6H), 1.25 (m, 28H), 1.1 (m, 6H), 
0.9 (t, 3H). 
Dihexanyl monostearin is prepared by melting 775.5 g (4.32 moles) 
1-glycerol-rac-monostearin obtained from Spectrum Chemicals (Lot # FC026) 
in a 2-L reaction flask equipped with a magnetic stirrer, boiling chips, 
heating mantle, thermometer, and reflux condenser prior to adding 775.5 g 
(2.16 moles) hexanoic anhydride (Aldrich Chemicals). The reaction flask is 
heated to 250.degree. C. for 8 hours at atmospheric pressure, and the 
hexanoic acid side product is removed by vacuum distillation at &gt;1 mm Hg, 
70.degree. C. The yield of distillate is quantitative. The product is 
passed through a falling film still equipped with mesitylne as the boiling 
solvent (168.degree. C., &lt;1 mm Hg) and steam deodorized at 210.degree. C., 
&lt;1 mm Hg. The yield is 2.12 moles (97.9%) of a golden yellow very soft 
solid having a DSC melting point of 13.degree. C. NMR in CDCl.sub.3 
(chemical shifts in ppm) indicates 99% product: 5.25 (m, 1H), 4.3 (dd, 
2H), 4.15 (dd, 2H), 2.3 (m, 6H), 1.6 (m, 6H), 1.25 (m, 36H), 0.9 (t, 3H). 
Dioctanyl monostearin is prepared by melting 200 g (0.56 moles) 
1-glycerol-rac-monostearin obtained from Spectrum Chemicals (Lot # FC026) 
in a 1-L reaction flask equipped with a magnetic stirrer, boiling chips, 
heating mantle, thermometer, and reflux condenser prior to adding 316.7 g 
(1.17 moles) octanoic anhydride (American Tokyo Kasei Inc). The reaction 
flask is heated to 250.degree. C. for 10 hours at atmospheric pressure, 
and the octanoic acid side product is removed by vacuum distillation at 
100 mm Hg, 160.degree. C. The yield of distillate is quantitative. The 
product is passed through a falling film still equipped with mesitylne as 
the boiling solvent (168.degree. C., &lt;1 mm Hg) and then steam deodorized 
at 210.degree. C., &lt;1 mm Hg. The yield is 320.2 g (0.52 moles, 93.6%) of a 
brown solid having a capillary melting point of 38.degree.-41.degree. C. 
and a DSC melting point of 37.degree. C. NMR in CDCl.sub.3 (chemical 
shifts in ppm) indicate 97.8% product: 5.25 (m, 1H), 4.3 (dd, 2H), 4.15 
(dd, 2H), 2.3 (m, 6H), 1.6 (m, 6H), 1.25 (m, 36H), 0.9 (t, 9H). 
Dicapryl monostearin is prepared by melting 269 g (0.75 moles) 
1-glycerol-rac-monostearin obtained from Spectrum Chemicals (Lot # FC026) 
in a 3-L reaction flask equipped with a magnetic stirrer, boiling chips, 
heating mantle, thermometer, and reflux condenser prior to adding 489.8 g 
(1.5 moles) decanoic (capric) anhydride (TCI Chemicals, lot FC 001). The 
reaction flask is heated to 200.degree. C. for 10 hours at atmospheric 
pressure, and the capric acid side product is removed by vacuum 
distillation at 100 mm Hg, 160.degree. C. The yield of distillate is 
quantitative. The brown soft solid product is passed through a falling 
film still equipped with mesitylne as the boiling solvent (168.degree. C., 
&lt;1 mm Hg) and then steam deodorized at 210.degree. C., &lt;1 mm Hg. The yield 
is 429.98 g (0.64 moles, 85.9%) of a golden yellow soft solid having a DSC 
melting point of 35.7.degree. C. and a capillary melting point of 
31.degree.-33.degree. C. NMR in CDCl.sub.3 (chemical shifts in ppm) 
indicates 98% product: 5.25 (m, 1H), 4.3 (dd, 2H), 4.15 (dd, 2H), 2.3 (m, 
6H), 1.6 (m, 6H), 1.25 (m, 36H), 0.9 (t, 9H). 
Dilauryl monostearin is prepared by melting 11.65 g (0.03 moles) 
1-glycerol-rac-monostearic obtained from Spectrum Chemicals (Lot # FC026) 
in a 200-mL reaction flask equipped with a magnetic stirrer, boiling 
chips, heating mantle, thermometer, and reflux condenser prior to adding 
25 g (0.065 moles) lauric anhydride (TCI Chemicals). The reaction flask is 
heated to 200.degree. C. for 10 hours at atmospheric pressure, and the 
capric acid side product is removed by vacuum distillation at &lt;5 mm Hg, 
180.degree. C. The yield of distillate is quantitative. The product is 
passed through a falling film still equipped with mesitylne as the boiling 
solvent (168.degree. C., &lt;1 mm Hg) and then steam deodorized at 
210.degree. C., &lt;1 mm Hg. The yield is 20.1 g (0.58 moles, 4.9%) of a 
golden yellow solid having a DSC melting point of 38.7.degree. C. and a 
capillary melting point of 33.degree.-36.degree. C. NMR in CDCl.sub.3 
(chemical shifts in ppm) indicates 98% product: 5.25 (m, 1H), 4.3 (dd, 
2H), 4.15 (dd, 2H), 2.3 (m, 6H), 1.6 (m, 6H), 1.25 (m, 36H), 0.9 (t, 9H). 
The data show a progressive decrease in melting point from 73.degree. C. 
for the beta form of tristearin to 38.7.degree. C. for dilauryl 
monostearin to 35.degree.-36.degree. for didecanyl monostearin to 
13.degree. C. for dihexanyl monostearin. This result can be correlated 
with generally expected decreases in melting points with decreasing sizes 
of the molecules. However, as the chain length is further decreased, the 
melting point surprisingly rises: 21.degree. for dibutyryl monostearin, 
24.degree. C. for dipropionyl monostearin, and 38.degree. C. for diacetyl 
monostearin. 
The low melting behavior of the dihexanyl derivative is in agreement with 
previously reported data wherein the C.sub.6 triglycerides were found to 
have minimum melting points in the C.sub.18 C.sub.n C.sub.18 and C.sub.n 
C.sub.n C.sub.18 series, n=2 to 18 (Jackson, et al., and Jackson and 
Lutton, cited above). 
Example 39 
This example compares and contrasts-cocoa butter with various low calorie 
triglycerides in chocolate coating compositions. The DSC melting profile 
of tempered cocoa butter control (), which hardens into a slightly waxy 
form after several months (), is compared with quench cooled cocoa butter 
() in FIG. 1. 
The coatings are prepared by mixing equal parts confectioner's sugar, cocoa 
powder, and test fat thoroughly at 55.degree. to 65.degree. C. with 0.5% 
by weight lecithin. The mixture is then poured into molds and allowed to 
cool to ambient temperature or refrigerated. 
A triglyceride mixture is prepared by the interesterification of 4.5 moles 
triacetin with 1.0 mole hydrogenated canola as outlined in Example 20. The 
resulting mixture was determined by SFC to contain 70% SSL/SLS, 27% 
SLL/LSL, and 3% LLL. A chocolate coating prepared with this fat had a DSC 
melting profile () and mouthfeel similar to a coating prepared with cocoa 
butter () on the first day, but hardened over time as illustrated in FIG. 
2 (11 days, (); 17 days, (). The coating had the mouthfeel of candlewax 
after only a few days at room temperature. 
Diacetostearin was prepared by the direct esterification of 97% glycerol 
monostearate with acetic anhydride as outlined in Example 3. The resulting 
mixture was determined by SFC to contain less than 5% SLL/LSL and LLL. A 
chocolate coating prepared with this fat had a melting profile and 
mouthfeel similar to a coating made with cocoa butter. The test coating 
hardened very slowly over a period of a year to a slightly waxy form. No 
bloom was noticeable after 18 months at room temperature, and the flavor 
did not change compared to a control held in the freezer in a sealed 
container. 
Hydrogenated canola was interesterified with triacetin and tripropionin as 
described in Example 24 in a ratio of 1:2:2.5. The resulting mixture was 
determined by SFC to contain 71% SSL/SLS, 27% SLL/LSL, and 2% LLL. As 
depicted in FIG. 3, a chocolate coating prepared with this fat had a DSC 
melting profile () similar to a coating made with cocoa butter (). The 
test coating stabilized to a slightly higher melting form after two days 
(), which persisted over the course of the study. The mouthfeel was 
acceptable, but the coating was soft. In addition, after 20 days at 
75.degree. F., a whitish bloom appeared that grew worse as time passed. 
The bloom was scraped from the surface, subjected to DSC and SFC analysis, 
and found to contain mostly SLL/LSL species. 
A desirable low calorie triglyceride mixture was prepared by 
interesterifying 11 moles triacetin and 1 mole tripropionin with 
hydrogenated canola as outlined in Example 36. The resulting mixture was 
determined by SFC to contain 85% SSL/SLS, 14.5% SLL/LSL, and 0.5% LLL. 
FIG. 4 shows that a coating prepared from this mixture () is lightly 
softer, but similar to a coating prepared with cocoa butter (). The 
coating hardens somewhat over time, but didn't become waxy; it has a lower 
DSC melting profile than cocoa butter after a 3-month storage at either 
75.degree. F. or 65.degree. F. No trace of bloom was observed in samples 
stored at 75.degree. F. after 3 months, and the odor and flavor remained 
very good. 
Example 40 
This example compares and contrasts cookies having a shortening component 
formulated with low calorie triglycerides of this invention and control 
cookies formulated with an all purpose vegetable shortening 
(Centrasoy.TM.). 
Reduced calorie fat mixtures are prepared as described in Examples 24 and 
36 using interesterification mixtures containing the following different 
reactant molar ratios of hydrogenated canola:tripropionin:triacetin and 
analyzed using SFC to determine the SSL/SLS, SLL/LSL, and LLL components 
as described in Example 21: 
______________________________________ 
Mixture SSL/SLS SLL/LSL LLL 
______________________________________ 
Mixture B from 1:1:11 
82.8 16.1 1.1 
Mixture C from 1:11:1 
84.8 14.41 0.8 
Mixture D from 1:3:9 
87.9 11.6 0.5 
Mixture E from 1:6:6 
84.4 13.8 1.8 
Mixture F from 1:9:3 
88.0 11.4 0.7 
______________________________________ 
The solid fat index for each mixture is measured using DSC. The area under 
the melting peak curves are integrated to give percent liquid at the 
desired temperatures of 0.degree. C., 10.degree. C., 21.1.degree. C., 
26.7.degree. C., 33.3.degree. C., and 37.8.degree. C. These values are 
then converted to percent solids. Using this methodology, the data are 
obtained are plotted in FIG. 5, with the control depicted as mixture B as 
, mixture C as , mixture D as , mixture E as and mixture F as . It can be 
seen that at room temperature, mixtures C and F are closest to the control 
shortening value of about 50% solids. 
______________________________________ 
grams 
______________________________________ 
To prepare the cookies, mix 
fine granulated sugar 
72.0 
brownulated brown sugar 
22.5 
nonfat dry milk 
2.3 
salt 2.8 
sodium bicarbonate 
2.3 
and then add 
control or test shortening 
90.0. 
Add high fructose corn syrup 
3.4 
then ammonium bicarbonate 
1.1 
and vanilla extract 0.34 
to water calculated* 
and add the water mixture to the shortening mixture. 
Add flour calculated* 
______________________________________ 
*g flour = {(10013% moisture basis)/(100flour moisture %) 
*225 g water = 225 g - g flour added + 49.5 
Sheet and cut the dough according to AACC Method 10-22. Bake at 400.degree. 
F. for 10 minutes in a National reel test bake oven. 
FNT *g flour={(100-13% moisture basis)/(100-flour moisture %)}*225 g g 
water=225 g-g flour added+49.5 
Dough viscosity is measured using a Stevens-LFRA.TM. texture analyzer. 
Immediately after preparing the dough, 109 grams are added to the LFRA cup 
and compressed to a constant volume. A spherical probe is then plunged 
into the dough 15 mm at a rate of 2 mm/sec. Five measurements are taken 
for each dough and the average load value (grams) is reported. Using this 
method, cookie dough made using the control shortening had a LFRA value of 
112; using mixture B, 1105; using mixture C, 180; using mixture D, 717; 
using mixture E, 296; and using mixture F, 136. Desirable processability 
LFRA values fall between about 100 and about 300, so that mixtures C, E, 
and F are acceptable shortenings in this cookie recipe, but mixtures B and 
D (high in acetic acid residues) make the dough too stiff. 
During baking, the dough blank weights and cookie weights are measured and 
recorded. The following equation is then used to calculate the percent 
weight loss during baking: 
EQU weight loss=100*(dbw-cw)/dbw 
where dbw=dough blank weight and cw=cookie weight. Final cookie moisture 
measurements are made using a Computrac.TM. set at 150.degree. C. Three 
runs of each sample are tested and an average moisture in % is recorded. 
Using this methodology, the following data are obtained: 
______________________________________ 
sample weight loss 
moisture 
______________________________________ 
control 12.32 5.65 
B 9.27 7.59 
C 8.60 8.56 
D 10.51 10.60 
E 9.34 7.68 
F 6.60 9.62 
______________________________________ 
All the test compounds have higher moisture, i.e., lower weight loss during 
baking, than the control. 
After baking, the cookies are measured. Using a micrometer, the cookie 
diameter/spread (mm) are measured on at least 3 cookies in 4 locations. An 
average value is obtained and reported as an average cookie diameter. Four 
cookies are then stacked and the stack height is measured. Average cookie 
height is then obtained by dividing by the number of cookies. Using these 
measurements the following data are obtained: 
______________________________________ 
sample diameter (mm) 
height (mm) 
______________________________________ 
control 82.65 9.22 
B 80.09 15.52 
C 70.84 11.76 
D 73.40 14.44 
E 71.23 13.59 
F 71.46 10.17 
______________________________________ 
All the test shortenings have smaller diameters, but higher stack heights, 
than the control. Among the materials tested, those with more propionic 
acid residues exhibited somewhat less spread and those with less propionic 
acid residues achieved greater height. 
Product color is evaluated using a Minolta Chroma.TM. meter model CR-210 to 
measure L, a rating of light to dark (&lt;.about.30 is dark); a, a sense of 
intensity of hue and a measure of red-green; and b, a sense of intensity 
of chroma and a measure of yellow-blue (roughly comparable to Hunter L, a, 
and b values). Desirable cookies exhibit red a values and yellow b values. 
Three cookies are measured three times and averaged for both top and 
bottom colors. Using this technique, the following data are obtained: 
______________________________________ 
sample TOP: L,a,b BOTTOM: L,a,b 
______________________________________ 
control 65.09, 6.11, 33.17 
45.46, 14.93, 29.44 
B 63.45, 7.03, 31.49 
42.78, 16.63, 30.70 
C 62.44, 6.75, 30.68 
45.41, 15.11, 31.71 
D 63.60, 6.10, 30.30 
43.10, 15.98, 31.11 
E 56.80, 9.29, 30.11 
39.76, 15.98, 28.94 
F 61.78, 6.54, 31.08 
45.66, 15.82, 30.96 
______________________________________ 
With the exception of sample E, which produced a darker cookie, there are 
no significant differences in any of the color values. 
Texture of the baked cookies is evaluated using an Instron.TM. 4501 
Universal Testing machine, which punctures the cookies and measures 
resistance to a small probe. 
Values for stress and moduli, which can be correlated with hardness, 
fracturability and/or brittleness, are calculated based on the resistant 
force versus distance. Using this technique, the following data are 
obtained: 
______________________________________ 
sample stress (kg/mm.sup.2) 
moduli (kg/mm.sup.2) 
______________________________________ 
control 0.435 8.07 
B 0.638 17.17 
C 0.293 9.20 
D 0.115 3.15 
E 0.168 6.31 
F 0.154 4.69 
______________________________________ 
The varying degrees of stress and moduli obtained suggest that textural 
attributes from cake-like to a dense snap cookie can be achieved. 
Example 41 
Like Example 40 above, this example evaluates cookies having a shortening 
component formulated with low calorie triglycerides of this invention, 
except that the triglycerides are blends rather than interesterified 
mixtures. 
Low calorie chocolate chips are first prepared. Diacetyl stearin, 150 g, is 
melted and blended with 150 g cocoa powder, 150 g confectioner's sugar and 
4.5 g lecithin, deposited into nibs and processed into chips. 
A blend of 35% diacetyl stearin and 65% dipropionyl stearin, which had a 
broad DSC melting range between about -15.degree. and 40.degree. C., is 
employed in the cookie recipe of Example 40 and compared with an all 
purpose vegetable shortening control cookie. Before baking, 112.5 grams 
chocolate chips formulated as described above are mixed into the test 
dough; Wilbur's real chocolate chips are used in the control. The cookies 
are baked at 420.degree. for 10 minutes. 
The baking behavior is depicted in FIG. 6, which compares the control 
cookie with the low calorie dipropionyl stearin/diacetyl stearin 
shortening cookie. At the two minute mark, the low calorie dough blank 
started to spread in an unusual steplike pattern. The cookies achieved a 
fairly high rise at 3 minutes and did not start to spread out until almost 
4 minutes into the bake. Collapse occurred around the 5 minute mark and 
setting and browning began to occur at 6 minutes. The final cookie had a 
nice brown color with low spread and high stack height. Color analysis 
using the Minolta Chroma.TM. meter described in the previous Example gave 
an L value of 59.56, an a value of 8.04 and a b value of 34.1. The 
diacetyl stearin chocolate chips stood up well under baking. 
The experiment is repeated comparing control cookies with cookies having 
shortening components comprising diacetyl stearin and either dibutyrl 
stearin or dipropionyl stearin. FIG. 7 shows DSC solid fat indices of 
different blends of diacetyl stearin with dipropionyl or dibutyryl stearin 
compared with a vegetable oil shortening control (). In the figure, is a 
1:1, is a 1:2 and is a 2:1 blend of diacetyl stearin and dibutyryl 
stearin; is a 1:1, and , a 4:1 blend of diacetyl stearin and dipropionyl 
stearin. 
Using the same control cookies containing an all purpose vegetable 
shortening and real Wilbur's chocolate chips, cookies formulated with a 
shortening comprising diacetyl stearin and dibutyryl stearin blended in 
equal proportions and diacetyl stearin chocolate chips (recipe G), and 
cookies formulated with a shortening comprising diacetyl stearin and 
dipropionyl stearin blended in equal proportions and diacetyl stearin 
chocolate chips (recipe H) are prepared and baked. 
Geometric and color measurements using the methodology of the above Example 
yielded the following data: 
______________________________________ 
recipe stack height (mm) 
width (mm) color (L,a,b) 
______________________________________ 
control 
1.125 8.1 56.51, 6.99, 27.81 
G 1.250 7.0 51.97, 10.84, 29.82 
H 1.125 7.5 57.43, 8.23, 30.24 
______________________________________ 
The control cookies came out flat and pale. The recipe G cookies required 
11 minutes to bake (instead of 10) and came out dark and mottled, with 
high stack height and little spread. The recipe H cookies had good stack 
height, good spread and good color. 
Example 42 
Cookies. 
Another cookie batch is prepared by mixing 
______________________________________ 
Ingredient grams 
______________________________________ 
Granulated Sugar 
12.8 
Brownulated Brown Sugar 
4.0 
Nonfat Dry Milk 0.4 
Salt 0.5 
Sodium Bicarbonate 
0.4 
A Dibutylstearin (35%) and 
16.0 
Corn Oil (65%) Blend 
To this is added 
Water 8.8 
High Fructose Corn Syrup 
0.6 
Ammonium Bicarbonate 
0.2 
Then Flour 40.0 
______________________________________ 
The dough is sheeted, cut and baked in the usual manner. 
Example 43 
Ice Cream. 
Chocolate ice cream is prepared by mixing 
______________________________________ 
Ingredient parts 
______________________________________ 
Water 60.6 
Example 37 Triglyceride Mixture B 
10.0 
Nonfat Dry Milk 10.0 
Sugar 10.0 
Corn Syrum 6.0 
Dricol .TM. Texture Enhancer 
0.3 
Cocoa Light 3.0 
Lecithin 0.1 
______________________________________ 
The ingredients are heated to pasturize, then cooled slightly, homogenized, 
and pumped into a heat exhanger whereupon the temperature is rapidly 
reduced. After the initiation of fat crystallization, the mixture is 
frozen. 
Example 44 
Cream Filling. 
To make a cream filling, combine 
______________________________________ 
Ingredient grams 
______________________________________ 
Sugar (6.times.) 376 
with Example 2 Diacetyl Stearin 
160 
Example 14 Dipropionyl Stearin 
24 
Example 36 Dihexanyl Stearin 
14 
Lecithin 2 
and Vanilla 0.3 
______________________________________ 
The filling had a smooth texture and mouthfeel and a solids content of 90% 
at 50.degree. F., 78% at 70.degree. F., 60% at 80.degree. F., 15% at 
92.degree. F., and 0% at 100.degree. F., which remained stable a week at 
room temperature. 
Example 45 
Sandwich Cookies. 
Basecakes may be prepared by combining parts 
______________________________________ 
parts 
______________________________________ 
Flour 48.0 
High Fructose Corn Syrup 
12.0 
Sugar (6.times.) 10.0 
Example 24 1:2.5:2.5 Triglyceride Mixture 
10.0 
Dutched Cocoa 5.0 
Corn Syrup (42 D.E.) 3.0 
Dextrose 2.0 
Frozen Whole Eggs 2.0 
Salt 0.3 
Sodium Bicarbonate 0.2 
Lecithin 0.2 
Vanilla 0.2 
Ammonium Bicarbonate 0.1 
Water 7.0 
______________________________________ 
mixing well, rotary molding, baking and cooling. Sandwich cookies are 
prepared by filling the basecakes with the filler of previous Example 44 
in a weight ratio of 100 parts basecake to 40.5 parts filler. 
The cookies may, optionally, be enrobed with a coating prepared by blending 
150 g melted diacetyl stearin, 150 g dutched cocoa powder, 150 g 
confectioner's sugar and 4.5 g lecithin. 
Example 46 
Shortening. 
A shortening may be prepared by interesterifying 2 moles of tributyrin with 
1 mole of hydrogenated canola as outlined in Example 20. 
Example 47 
Margarine. 
A stick margarine may be prepared by emulsifying 
______________________________________ 
parts 
______________________________________ 
Oil Phase Ingredients 
Example 20 1:2.5 40 
Triglyceride Mixture 
Liquid Corn Oil 40 
Lecithin 0.3 
Mono- and Di-glycerides 
0.21 
Margarine Flavor and Color 
0.0062 
with Aqueous Phase Ingredients 
Water 16.4 
Whey 1.00 
Salt 2.00 
Sodium Benzoate 0.086 
______________________________________ 
and passing the emulsion through a cooled, scraped-surface heat exchanger 
in the usual process. 
Example 48 
Low Fat Spread. 
A 60% table spread may be prepared by emulsifying 
______________________________________ 
parts 
______________________________________ 
Oil Phase Ingredients 
A 65:35 Blend of Corn Oil: 
59.58 
Example 20 1:1.25 Triglycerides 
Lecithin 0.20 
Distilled Monoglycerides from 
0.20 
Unhydrogenated Sunflower Oil 
Beta-carotene and Vitamin 
0.005 
A Palmitate in Corn Oil 
Flavor 0.010 
ith Aqueous Phase Ingredients 
Water 37.86 
Salt 2.00 
Potassium Sorbate 0.10 
Phosphoric Acid 0.04 
______________________________________ 
and passing the emulsion through a cooled, scraped-surface heat exchanger 
in the usual process. 
Example 49 
Low Fat Spread. 
A 40% table spread may be prepared by emulsifying 
______________________________________ 
parts 
______________________________________ 
Oil Phase Ingredients 
A 75:25 Blend of Corn Oil: 
39.38 
Example 14 Triglycerides 
Lecithin 0.10 
Distilled Monoglycerides from 
0.50 
Unhydrogenated Sunflower Oil 
Flavor 0.010 
with Aqueous Phase Ingredients 
Water 57.86 
Salt 2.00 
Potassium Sorbate 0.10 
Calcium Disodium EDTA 0.006 
______________________________________ 
and passing the emulsion through a cooled, scraped-surface heat exchanger 
in the usual process. 
Example 50 
Spray Oil. 
A spray oil may be prepared by interesterifying 12 moles tributyrin with 1 
mole of hydrogehated canola as outlined in Example 20. 
Example 51 
Low calorie triglycerides of this invention bearing two short residues and 
one long, saturated moiety include the following example compounds: 
1-acetyl-3-palmitoyl-2-propionyl glyceride 
2-acetyl-1-palmitoyl-3-propionyl glyceride 
2-acetyl-1-propionyl-3-stearoyl glyceride 
1-acetyl-2-propionyl-3-stearoyl glyceride 
1-acetyl-3-arachidoyl-2-propionyl glyceride 
2-acetyl-1-arachidoyl-3-propionyl glyceride 
1-acetyl-3-behenoyl-2-propionyl glyceride 
2-acetyl-1-behenoyl-3-propionyl glyceride 
1-acetyl-2-butyryl-3-palmitoyl glyceride 
2-acetyl-1-butyryl-3-palmitoyl glyceride 
2-acetyl-1-butyryl-3-stearoyl glyceride 
1-acetyl-2-butyryl-3-stearoyl glyceride 
1-acetyl-3-arachidoyl-2-butyryl glyceride 
2-acetyl-1-arachidoyl-3-butyryl glyceride 
1-acetyl-3-behenoyl-2-butyryl glyceride 
2-acetyl-1-behenoyl-3-butyryl glyceride 
1-acetyl-3-palmitoyl-2-valeryl glyceride 
2-acetyl-1-palmitoyl-3-valeryl glyceride 
2-acetyl-1-stearoyl-3-valeryl glyceride 
1-acetyl-3-stearoyl-2-valeryl glyceride 
1-acetyl-3-arachidoyl-2-valeryl glyceride 
2-acetyl-1-arachidoyl-3-valeryl glyceride 
1-acetyl-3-behenoyl-2-valeryl glyceride 
2-acetyl-1-behenoyl-3-valeryl glyceride 
1-butyryl-3-palmitoyl-2-propionyl glyceride 
2-butyryl-1-palmitoyl-3-propionyl glyceride 
2-butyryl-1-propionyl-3-stearoyl glyceride 
1-butyryl-3-stearoyl-2-propionyl glyceride 
1-arachidoyl-2-butyryl-3-propionyl glyceride 
1-arachidoyl-3-butyryl-2-propionyl glyceride 
1-behenoyl-3-butyryl-2-propionyl glyceride 
1-behenoyl-2-butyryl-3-propionyl glyceride 
1-palmitoyl-2-propionyl-3-valeryl glyceride 
1-palmitoyl-3-propionyl-2-valeryl glyceride 
2-propionyl-1-stearoyl-3-valeryl glyceride 
1-propionyl-3-stearoyl-2-valeryl glyceride 
1-arachidoyl-2-propionyl-3-valeryl glyceride 
1-arachidoyl-3-propionyl-2-valeryl glyceride 
1-behenoyl-2-propionyl-3-valeryl glyceride 
1-behenoyl-3-propionyl-2-valeryl glyceride 
1-acetyl-2-palmitoyl-3-propionyl glyceride 
1-acetyl-3-propionyl-2-stearoyl glyceride 
1-acetyl-2-arachidoyl-3-propionyl glyceride 
1-acetyl-2-behenoyl-3-propionyl glyceride 
1-acetyl-3-butyryl-2-palmitoyl glyceride 
1-acetyl-3-butyryl-2-stearoyl glyceride 
1-acetyl-2-arachidoyl-3-butyryl glyceride 
1-acetyl-2-behenoyl-3-butyryl glyceride 
1-acetyl-2-palmitoyl-3-valeryl glyceride 
1-acetyl-2-stearoyl-3-valeryl glyceride 
1-acetyl-2-arachidoyl-3-valeryl glyceride 
1-acetyl-2-behenoyl-3-valeryl glyceride 
1-butyryl-2-palmitoyl-3-propionyl glyceride 
1-butyryl-2-stearoyl-3-propionyl glyceride 
2-arachidoyl-1-butyryl-3-propionyl glyceride 
2-behenoyl-1-butyryl-3-propionyl glyceride 
2-palmitoyl-1-propionyl-3-valeryl glyceride 
1-propionyl-2-stearoyl-3-valeryl glyceride 
2-arachidoyl-1-propionyl-3-valeryl glyceride 
2-behenoyl-1-propionyl-3-valeryl glyceride 
Low calorie triglyceride mixtures of this invention can also include the 
following example compounds: 
SSL Derivatives 
1,2-diacetyl-3-palmitoyl glyceride 
1,2-diacetyl-3-stearoyl glyceride 
1,2-diacetyl-3-arachidoyl glyceride 
1,2-diacetyl-3-behenoyl glyceride 
1-palmitoyl-2,3-dipropionyl glyceride 
1,2-dipropionyl-3-stearoyl glyceride 
1-arachidoyl-2,3-dipropionyl glyceride 
1-behenoyl-2,3-dipropionyl glyceride 
1,2-dibutyryl-3-palmitoyl glyceride 
1,2-dibutyryl-3-stearoyl glyceride 
1-arachidoyl-2,3-dibutyryl glyceride 
1-behenoyl-2,3-dibutyryl glyceride 
SLS Derivatives 
1,3-diacetyl-2-palmitoyl glyceride 
1,3-diacetyl-2-stearoyl glyceride 
1,3-diacetyl-2-arachidoyl glyceride 
1,3-diacetyl-2-behenoyl glyceride 
2-palmitoyl-1,3-dipropionyl glyceride 
1,3-dipropionyl-2-stearoyl glyceride 
2-arachidoyl-1,3-dipropionyl glyceride 
2-behenoyl-1,3-dipropionyl glyceride 
1,3-dibutyryl-2-palmitoyl glyceride 
1,3-dibutyryl-2-stearoyl glyceride 
2-arachidoyl-1,3-dibutyryl glyceride 
2-behenoyl-1,3-dibutyryl glyceride 
LLS Derivatives 
1-acetyl-2,3-dipalmitoyl glyceride 
1-acetyl-2,3-distearoyl glyceride 
1-acetyl-2,3-diarachidoyl glyceride 
1-acetyl-2,3-dilignoceroyl glyceride 
1-acetyl-2,3-dibehenoyl glyceride 
1,2-dipalmitoyl-3-propionyl glyceride 
1-propionyl-2,3-distearoyl glyceride 
1,2-diarachidoyl-3-propionyl glyceride 
2-propionyl-1,3-distearoyl glyceride 
1,2-dibehenoyl-3-propionyl glyceride 
1,2-diarachidoyl-3-butyryl glyceride 
1-butyryl-2,3-dipalmitoyl glyceride 
1-butyryl-2,3-dicerotoyl glyceride 
1-acetyl-2-palmitoyl-3-stearoyl glyceride 
1-acetyl-3-palmitoyl-2-stearoyl glyceride 
1-acetyl-3-arachidoyl-2-palmitoyl glyceride 
1-acetyl-2-arachidoyl-3-palmitoyl glyceride 
1-acetyl-3-behenoyl-2-palmitoyl glyceride 
1-acetyl-2-behenoyl-3-palmitoyl glyceride 
1-acetyl-2-arachidoyl-3-stearoyl glyceride 
1-acetyl-3-behenoyl-2-stearoyl glyceride 
1-acetyl-3-arachidoyl-2-stearoyl glyceride 
1-acetyl-2-behenoyl-3-stearoyl glyceride 
1-acetyl-2-arachidoyl-3-behenoyl glyceride 
1-acetyl-3-arachidoyl-2-behenoyl glyceride 
1-palmitoyl-3-propionyl-2-stearoyl glyceride 
1-palmitoyl-1-propionyl-3-stearoyl glyceride 
1-arachidoyl-2-palmitoyl-3-propionyl glyceride 
1-behenoyl-2-palmitoyl-3-propionyl glyceride 
2-arachidoyl-1-palmitoyl-3-propionyl glyceride 
2-behenoyl-1-palmitoyl-3-propionyl glyceride 
1-arachidoyl-3-propionyl-2-stearoyl glyceride 
1-behenoyl-3-propionyl-2-stearoyl glyceride 
2-arachidoyl-1-propionyl-3-stearoyl glyceride 
2-behenoyl-1-propionyl-3-stearoyl glyceride 
1-butyryl-2-palmitoyl-3-stearoyl glyceride 
2-arachidoyl-1-butyryl-3-palmitoyl glyceride 
1-butyryl-3-palmitoyl-2-stearoyl glyceride 
1-arachidoyl-3-butyryl-2-palmitoyl glyceride 
2-behenoyl-1-butyryl-3-palmitoyl glyceride 
1-behenoyl-3-butyryl-2-palmitoyl glyceride 
1-arachidoyl-3-butyryl-2-stearoyl glyceride 
2-arachidoyl-1-butyryl-3-stearoyl glyceride 
2-behenoyl-1-butyryl-3-stearoyl glyceride 
1-behenoyl-3-butyryl-2-stearoyl glyceride 
1-arachidoyl-2-behenoyl-3-butyryl glyceride 
2-arachidoyl-1-behenoyl-3-butyryl glyceride 
LSL Derivatives 
2-acetyl-1,3-dipalmitoyl glyceride 
2-acetyl-1,3-distearoyl glyceride 
2-acetyl-1,3-diarachidoyl glyceride 
2-acetyl-1,3-dibehenoyl glyceride 
1,3-diarachidoyl-2-propionyl glyceride 
1,3-dibehenoyl-2-propionyl glyceride 
2-butyryl-1,3-dipalmitoyl glyceride 
1,3-dipalmitoyl-2-propionyl glyceride 
1,3-diarachidoyl-2-butyryl glyceride 
1,3-dibehenoyl-2-butyryl glyceride 
2-acetyl-1-palmitoyl-3-stearoyl glyceride 
2-acetyl-1-behenoyl-3-palmitoyl glyceride 
2-acetyl-1-arachidoyl-3-palmitoyl glyceride 
2-acetyl-1-arachidoyl-3-stearoyl glyceride 
2-acetyl-1-behenoyl-3-stearoyl glyceride 
1-palmitoyl-2-propionyl-3-stearoyl glyceride 
1-arachidoyl-3-palmitoyl-2-propionyl glyceride 
1-behenoyl-3-palmitoyl-2-propionyl glyceride 
1-behenoyl-2-propionyl-3-stearoyl glyceride 
1-arachidoyl-3-behenoyl-2-propionyl glyceride 
2-butyryl-1-palmitoyl-3-stearoyl glyceride 
1-arachidoyl-2-butyryl-3-palmitoyl glyceride 
1-behenoyl-2-butyryl-3-palmitoyl glyceride 
1-arachidoyl-2-butyryl-3-stearoyl glyceride 
1-behenoyl-2-butyryl-3-stearoyl glyceride 
1-arachidogyl-3-behenoyl-2-butyryl glyceride 
The above description is for the purpose of teaching the person of ordinary 
skill in the art how to practice the present invention, and it is not 
intended to detail all those obvious modifications and variations of it 
which will become apparent to the skilled worker upon reading the 
description. It is intended, however, that all such obvious modifications 
and variations be included within the scope of the present invention, 
which is defined by the following claims.