Ethoxylated sugar and sugar alcohol esters useful as fat substitutes

The present invention relates to a fat substitute comprising an ethoxyloted sugar or sugar alcohol sucrose fatty acid ester. Between 1 and about 50 alkoxyl groups are attached by ether linkages to each polyol molecule. Each ethoxylated polyol is esterified with between about 6 and about 8 fatty acid groups, the fatty acids containing between about 2 and about 24 carbon atoms. The invention also relates to a low calorie fat-containing food composition which comprises: (a) non-fat ingredients; and (b) fat ingredients, from about 10% to about 100% by weight of said fat ingredients consisting essentially of the above-described fat substitute.

TECHNICAL FIELD 
The present invention relates to the field of low calorie fat and oil 
substitutes. Specifically, the invention relates to fatty acid polyesters 
of alkoxylated sugars and sugar alcohols. The alkoxyl groups are derived 
from cyclic ethers containing 2 to 4 carbon atoms, particularly epoxides. 
The compounds of the invention have been found to be useful for replacing 
triglyceride fats in low calorie fat-containing food compositions. 
BACKGROUND OF THE INVENTION 
The consumption of large amounts of triglyceride fats has been linked to 
various health problems. For example, one of the most common metabolic 
problems among people today is obesity. This condition is primarily due to 
ingestion of a greater number of calories than are expended. Fat is the 
most concentrated form of energy in the diet, with each gram of fat 
supplying approximately nine calories, and triglyceride fats constitute 
about 90% of the total fat consumed in the average diet. 
The National Institutes of Health Consensus Development Conference, 
"Lowering Blood Cholesterol to Prevent Heart Disease," JAMA, Vol. 253, No. 
14, pp. 2080-2086 (1985), concluded that elevation of blood cholesterol 
levels is a major cause of coronary artery disease, and recommended a 
reduction in the amount of fat eaten to reduce blood serum cholesterol 
levels. 
Hence, there is a need for ways to reduce the amount of triglyceride fats 
in the diet, in order to reduce the health risks associated with these 
fats. 
Numerous fat substitutes are known to the art. A review of some of the 
approaches tried for replacing fats and oils is given in an article by 
Haumann, "Getting the Fat Out," JAOCS, Vol. 63, No. 3, pp. 278-288 (March 
1986). Various approaches and products that have been suggested for 
replacement of the fat content of foods are examined in LaBarge, "The 
Search for a Low-Caloric Oil," Food Technology, pp. 84-90 (January 1988). 
A partial list of some of the reduced calorie fat substitutes known to the 
art includes the following: fatty alcohol esters of polycarboxylic acids 
(U.S. Pat. No. 4,508,746 to Hamm, issued Apr. 2, 1985); fatty polyethers 
of polyglycerol (U.S. Pat. No. 3,932,532 to Hunter et al., issued Jan. 13, 
1976) (food use disclosed in German Patent 207,070, issued February 15, 
1984); ethers and ether-esters of polyols containing the neopentyl moiety 
(U.S. Pat. No. 2,962,419 to Minich, issued Nov. 29, 1960); fatty alcohol 
diesters of dicarboxylic acids such as malonic and succinic acid (U.S. 
Pat. No. 4,582,927 to Fulcher, issued Apr. 15, 1986); triglyceride esters 
of alpha branched chain-alkyl carboxylic acids (U.S. Pat. No. 3,579,548 to 
Whyte, issued May 18, 1971); fatty acid diglyceride, diesters of dibasic 
acids (U.S. Pat. No. 2,874,175 to Feuge et al.); polyorganosiloxanes 
(European Patent Application 205,273 to Frye); alpha-acylated glycerides 
(U.S. Pat. No. 4,582,715 to Volpenhein); medium chain triglycerides; 
highly esterified polyglycerol esters; acetin fats; plant sterol esters; 
N-Oil; polyoxyethylene esters; jojoba esters; mono/diglycerides of fatty 
acids; and mono/diglycerides of short-chain dibasic acids. 
Sugar and sugar alcohol fatty acid polyesters are disclosed for use as fat 
substitutes in U.S. Pat. No. 3,600,186 to Mattson et al., issued Aug. 17, 
1971. However, there is no suggestion that alkoxylated sugar and sugar 
alcohol polyesters are also suitable as fat substitutes. 
Alkoxylated sugars and sugar alcohols are known to the art for use in 
making urethanes and polyurethanes. For example, U.S. Pat. No. 4,332,936 
to Nodelman, issued June 1, 1982, discloses an improved method for making 
oxyalkylated polyols (including certain sugars and sugar alcohols) by 
adding a solid initiator to the reaction mixture. The products are said to 
be particularly suited for the production of rigid polyurethane foams. 
U.S. Pat. No. 3,317,508 to Winquist, Jr. et al., issued May 2, 1967, 
discloses a process for making alkylene oxide adducts of polyhydroxy 
organic compounds (including sugars) by utilizing novel ditertiary amino 
catalysts. 
U.S. Pat. No. 4,239,907 to Bedoit, Jr., issued Dec. 16, 1980, discloses the 
employment of a water-soluble initiator to make alkoxylated sucrose and 
sorbitol. The product is said to be useful in the production of urethane 
foams. U.S. Pat. No. 3,346,557 to Patton, Jr., et al., issued Oct. 10, 
1967, discloses another method for oxyalkylating polyols. While the 
above-mentioned Nodelman, Winquist, Bedoit, and Patton patents disclose 
alkoxylated sugars and sugar alcohols, they do not disclose the fatty acid 
esters of these compounds. 
Japanese Kokai Patent No. Sho 52[1977]-62216 to Nakamura et al., published 
May 23, 1977, discloses polyoxyalkylenated sucrose that is esterified with 
aliphatic acids having C.sub.8 to C.sub.22 saturated or unsaturated alkyl 
groups. However, the sucrose esters contain only 1 to 3 acid groups per 
sucrose molecule. The polyoxyalkylenated sucrose esters are said to be 
useful as nonionic surfactants. 
One of the main problems in attempting to formulate fat compounds that have 
decreased absorbability and thus low calorie properties is to maintain the 
desirable and conventional physical properties of edible fat. Thus, to be 
a practical low calorie fat, a compound must resemble conventional 
triglyceride fat, and have the same utility in various fat-containing food 
compositions such as shortening, margarine, cake mixes, and the like, and 
be useful in frying or baking. 
None of the above-mentioned references suggests that fatty acid polyesters 
of alkoxylated sugars and sugar alcohols are particularly suitable as low 
calorie fat substitutes for use in fat-containing food compositions. 
Alkoxylated sugars and sugar alcohols are known for making urethane foams, 
but there is no suggestion in the art of fatty acid esters of these 
compounds being suitable as fat substitutes. These compounds have now 
surprisingly been found to have organoleptic and other physical properties 
that make them well-suited as fat substitutes. This is surprising in view 
of the significant structural difference between the present compounds and 
sugar and sugar alcohol esters or triglycerides. 
Moreover, the compounds of the invention have now been found to be 
resistant to hydrolysis and therefore nondigestible. Accordingly, the 
compounds contain zero calories, in contrast to the nine calories per gram 
in triglyceride fats. 
It is, therefore, an object of the present invention to provide fat 
substitutes comprising fatty acid polyesters of alkoxylated sugars and 
sugar alcohols. 
It is another object of the present invention to provide fat substitutes 
that are resistant to hydrolysis and therefore nondigestible and 
noncaloric. 
It is a further object of the present invention to provide low calorie 
fat-containing food compositions containing these fat substitutes. 
These and other objects of the present invention will become evident from 
the disclosure herein. 
All parts, percentages and ratios used herein are by weight unless 
otherwise indicated. 
SUMMARY OF THE INVENTION 
The present invention relates to a fat substitute comprising a fatty acid 
ester of an alkoxylated polyol, where the polyol is a sugar or sugar 
alcohol. Between about 1 and about 50 alkoxyl groups are attached by ether 
linkages to each polyol molecule. Each alkoxylated polyol is esterified 
with between about 6 and about 8 fatty acid groups, the fatty acids 
containing between about 2 and about 24 carbon atoms. The alkoxyl groups 
are derived from cyclic ethers selected from propylene oxide, ethylene 
oxide, 1-butene oxide, cis-2-butene oxide, trans-2-butene oxide, 1-hexene 
oxide, tertbutylethylene oxide, cyclohexene oxide, 1-octene oxide, 
cyclohexylethylene oxide, styrene oxide, 1-decene oxide, 1-octadecene 
oxide, isobutylene oxide, epichlorohydrin, epibromohydrin, epiiodohydrin, 
perfluoropropylene oxide, cyclopentene oxide, 1-pentene oxide, oxetane, 
oxetane derivatives, and mixtures thereof. The invention also relates to a 
low calorie fat-containing food composition which comprises: (a) non-fat 
ingredients; and (b) fat ingredients, from about 10% to about 100% by 
weight of said fat ingredients consisting essentially of the 
above-described fat substitute.

DETAILED DESCRIPTION OF THE INVENTION 
The present invention relates to certain fatty acid polyesters of 
alkoxylated sugars and sugar alcohols which have now been surprisingly 
discovered to be useful as fat substitutes, particularly for use in low 
calorie fat-containing food compositions. The food compositions comprise: 
(a) non-fat ingredients; and (b) fat ingredients, from about 10% to 100% 
by weight of the fat ingredients consisting essentially of the alkoxylated 
sugar or sugar alcohol polyesters of the present invention. 
The compounds of the present invention (and fat-containing food 
compositions containing these compounds) have desirable physical 
properties and palatability compared to ordinary triglyceride fats and 
compositions containing same. However, these compounds have a 
substantially lower effective caloric value than triglyceride fats (zero 
calories/gram versus nine calories/gram) because they are not digested or 
absorbed in the intestinal tract. 
A. Definitions 
By "alkoxylated" sugars and sugar alcohols, as used herein, is meant that 
the sugars and sugar alcohols are reacted with cyclic ether compounds 
selected from the group consisting of propylene oxide, ethylene oxide, 
1-butene oxide, cis-2-butene oxide, trans-2-butene oxide, 1-hexene oxide, 
tert-butylethylene oxide, cyclohexene oxide, 1-octene oxide, 
cyclohexylethylene oxide, styrene oxide, 1-decene oxide, 1-octadecene 
oxide, isobutylene oxide, epichlorohydrin, epibromohydrin, epiiodohydrin, 
perfluoropropylene oxide, cyclopentene oxide, 1-pentene oxide, oxetane, 
oxetane derivatives, and mixtures thereof, to form hydroxyl terminated 
ether compounds. With the exception of oxetane and oxetane derivatives, 
these compounds are all epoxides. The ring structures of the compounds 
contain 2 to 4 carbon atoms and an oxygen atom. Preferred compounds for 
use herein are propylene oxide, ethylene oxide, and mixtures thereof. Most 
preferred is propylene oxide. These compounds and their chemistry are 
known to those skilled in the art. See, e.g., Encyclopedia of Polymer 
Science and Technology, 1st Ed., Vol. 6, 1,2-Epoxide Polymers, pp. 108, 
154, 186, 187, and 192, Interscience Publishers, New York (1967), and 2 nd 
Ed., Vol. 6, pp. 276-277 (1985); and Frisch, Cyclic Monomers. Vol. XXVI of 
the High Polymers Series, pp. 8-9, 54-59 and 100-102, Wiley-Interscience, 
New York (1972). 
By "alkoxyl groups", as used herein, is meant the cyclic ether compounds 
disclosed above after they have reacted with and become attached to a 
sugar or sugar alcohol through ether linkages. For example, propylene 
oxide reacts with sucrose to form propoxylated sucrose; the propylene 
oxide changes into a "propoxyl" group during the reaction. Similarly, 
ethylene oxide becomes an "ethoxyl" group. Hence, the alkoxyl groups are 
"derived from" the above-mentioned cyclic ether compounds. This is 
understood in the art; see, e.g., U.S. Pat. No. 4,264,478 of Seldner, 
issued Apr. 28, 1981, column 3, lines 31-43 (incorporated by reference 
herein). 
By "polyol", as used herein, is meant a sugar or sugar alcohol, or mixtures 
thereof. The term "sugar" is used herein in its conventional sense as 
generic to mono- and disaccharides. The term "sugar alcohol" is also used 
in its conventional sense as generic to the reduction product of sugars 
wherein the aldehyde or ketone group has been reduced to an alcohol. 
Suitable for use in the present invention are sugars and sugar alcohols 
containing at least 4 hydroxyl groups. The fatty acid ester compounds of 
the invention are prepared by reacting an alkoxylated monosaccharide, 
disaccharide or sugar alcohol with fatty acids as discussed below. 
Examples of suitable monosaccharides are those containing 4 hydroxyl groups 
such as xylose, arabinose, and ribose; the sugar alcohol derived from 
xylose, i.e., xylitol, is also suitable. The monosaccharide erythrose is 
not suitable for the practice of this invention since it only contains 3 
hydroxyl groups; however, the sugar alcohol derived from erythrose, i.e., 
erythritol, contains 4 hydroxyl groups and is thus suitable. Among 5 
hydroxyl-containing monosaccharides that are suitable for use herein are 
glucose, mannose, galactose, fructose, and sorbose. A sugar alcohol 
derived from sucrose, glucose, or sorbose, e.g., sorbitol, contains 6 
hydroxyl groups and is also suitable as the alcohol moiety of the fatty 
acid ester compound. Examples of suitable disaccharides are maltose, 
lactose, and sucrose, all of which contain 8 hydroxyl groups. Sucrose is 
especially preferred. 
B. Fatty Acid Polyesters of Alkoxylated Sugars and Sugar Alcohols 
A fat substitute according to the present invention comprises a fatty acid 
ester of an alkoxylated polyol, wherein: 
(a) the polyol is selected from the group consisting of sugars and sugar 
alcohols, and mixtures thereof, wherein the sugars and sugar alcohols 
contain at least 4 hydroxyl groups; 
(b) between 1 and about 50 alkoxyl groups are attached by ether linkages to 
each polyol molecule; 
(c) each alkoxylated polyol is esterified with between about 6 and about 8 
fatty acid groups; 
(d) the fatty acids contain between about 2 and about 24 carbon atoms; and 
(e) the alkoxyl groups are derived from cyclic ethers selected from the 
group consisting of propylene oxide, ethylene oxide, 1-butene oxide, 
cis-2-butene oxide, trans-2-butene oxide, 1-hexene oxide, 
tert-butylethylene oxide, cyclohexene oxide, 
1-octene oxide, cyclohexylethylene oxide, styrene oxide, 1-decene oxide, 
1-octadecene oxide, isobutylene oxide, epichlorohydrin, epibromohydrin, 
epiiodohydrin, perfluoropropylene oxide, cyclopentene oxide, 1-pentene 
oxide, oxetane, oxetane derivatives, and mixtures thereof. 
It has been discovered that each sugar or sugar alcohol group of the fat 
substitute must have attached to it through ether linkages between 1 and 
about 50 alkoxyl groups. Polyesters with higher degrees of alkoxylation 
will have more polyether character than is desirable in a fat substitute. 
The compounds contain at least one alkoxyl group; it is hypothesized that 
an alkoxylated structure may have even more resistance to hydrolysis (to 
an unexpectedly greater extent) than unalkoxylated sugar and sugar alcohol 
esters because placing the ester linkage farther away from the polyol 
makes it more difficult for lipase enzymes to handle these compounds and 
initiate digestion. Preferably, between about 8 and about 2 alkoxyl groups 
are attached to each polyol molecule, more preferably between about 8 and 
about 16. 
Moreover, attachment of fatty acid ester groups at the ends of the alkoxyl 
groups produces a large hydrophilic center in the compounds. As a result, 
it is believed that the compounds form better emulsions in the gut and 
thus are more compatible with the gastrointestinal tract so that fewer GI 
problems such as oil separation will occur. 
As is well known to the art, sugars and sugar alcohols contain varying 
numbers of attachment sites available for ether linkages with alkoxyl 
groups depending on their number of hydroxyl groups; for example, sucrose 
has eight attachment sites corresponding to its eight hydroxyl groups. 
Preferably, the number of alkoxyl groups attached by ether linkages to 
each attachment site of the sugar or sugar alcohol varies between about 1 
and about 4, more preferably between about 1 and about 2. When more than 
one alkoxyl group attaches to a single attachment site of the sugar or 
sugar alcohol, the alkoxyl groups are polymerized in the form of a chain. 
The chemistry of polymerization of alkoxyl groups is known to those 
skilled in the art. See, e.g., Frisch, Cyclic Monomers, Vol. XXVI of High 
Polymers Series, Wiley Interscience, New York, pp. 36-39 (1972); and 
Saunders and Frisch, Polyurethanes: Chemistry and Technology, Part I, 
Interscience Publishers, New York, pp. 32-43 (1962). 
The fatty acid groups of the present fat substitute are esterified to the 
alkoxylated sugar or sugar alcohol. Each alkoxylated polyol is esterified 
with between about 6 and about 8 fatty acid groups. Fatty acid esters of 
alkoxylated polyols with esterification less than six will begin to have 
surfactant-type properties making them unsuitable as fat substitutes. 
Complete esterification is more desirable to attain the desired 
organoleptic character in the alkoxylated sugar or sugar alcohol 
polyester. Accordingly, it is preferred that each alkoxylated polyol is 
esterified with about 8 fatty acid groups. 
The fatty acids are C.sub.2 to C.sub.24 in carbon chain length to impart 
the desired organoleptic character to the polyester compounds. Preferred 
fatty acids are C.sub.8 to C.sub.22, more preferred are C.sub.14 to 
C.sub.18, and most preferred are C.sub.18. Examples of such fatty acids 
include acetic, butyric, caprylic, capric, lauric, myristic, myristoleic, 
palmitic, palmitoleic, stearic, oleic, ricinoleic, linoleic, linolenic, 
eleostearic, arachidic, arachidonic, behenic, and erucic acid. The fatty 
acids can be derived from naturally occurring or synthetic fatty acids, 
and can be saturated or unsaturated, including positional or geometrical 
isomers (e.g., cis and trans isomers). Oleic acid is especially preferred, 
and stearic acid second most preferred. 
C. Methods for Making the Fatty Acid Polyesters of Alkoxylated Sugars and 
Sugar Alcohols 
For making the fat substitutes of the present invention, the starting 
material is an alkoxylat.de sugar or sugar alcohol. Union Carbide 
Corporation, Danbury, Conn., sells propoxylated sucrose under the trade 
name Niax.RTM. E-651 polyol. This compound is prepared by reacting 1 mole 
of sucrose with 14 moles of propylene oxide to form a propoxylated 
sucrose. A process for making propoxylated sucrose and other alkylene 
oxide adducts of polyhydroxy organic compounds is disclosed in U.S. Pat. 
No. 3,317,508 assigned to Union Carbide Corp., issued May 2, 1967 
(incorporated by reference herein); see, specifically, Example 1. The 
following patents (all incorporated by reference herein) also disclose 
methods for making various alkoxylated sugars and sugar alcohols: U.S. 
Pat. No. 4,332,936 to Nodelman, issued June 1, 1982; U.S. Pat. No. 
4,239,907 to Bedoit, Jr., issued Dec. 16, 1980; and U.S. Pat. No. 
3,346,557 to Patton, Jr. et al., issued Oct. 10, 1967. 
The alkoxylated sugar or sugar alcohol is esterified with fatty acids by 
any of a variety of general esterification methods well known to those 
skilled in the art. These methods include: acylation with a fatty acid 
chloride, acylation with a fatty acid anhydride, acylation with a fatty 
acid per se, and transesterification with another ester such as methyl, 
ethyl or glycerol. The preferred method is acylation with a fatty acid 
chloride, as disclosed in Example 1 hereinafter. 
Example 1 shows the preparation of a propoxylated sucrose octaoleate 
Niax.RTM. E-651 (34.1 grams) is first diluted in a solvent mixture of 50 
ml DMF and 100 ml pyridine. While this DMF/pyridine mixture is the 
preferred solvent, it is anticipated that other organic solvents known to 
those skilled in the art could also be used. This solution is charged to a 
flask equipped with a reflux condenser, dry N.sub.2 purge, and a magnetic 
stirrer. 
The Niax.RTM. E-651 solution is heated to a temperature between 40.degree. 
C. (104.degree. F.) and 45.degree. C. (113.degree. F.) while the flask is 
purged with nitrogen. While 40.degree.-45.degree. C. 
(104.degree.-113.degree. F.) is the preferred temperature range, the 
practical operating range can vary from 0.degree. C. (32.degree. F.) to 
the solvent reflux temperature; the upper limit will vary with the solvent 
composition (it is about 115.degree. C. (239.degree. F.) for the 
DMF/pyridine solvent). The reaction is preferably conducted under 
nitrogen. However, other inert gases can be used instead of nitrogen, such 
as helium or argon. 
Separately, oleoyl chloride (72.5 grams) is diluted in 200 ml of methylene 
chloride. Chlorides of other fatty acids besides oleic acid are also 
suitable for use in the present invention, but oleic acid is the most 
preferred fatty acid while stearic acid is second most preferred. Other 
suitable C.sub.2 to C.sub.24 fatty acids are described hereinabove. The 
preferred solvent for the fatty acid chloride is methylene chloride, but 
other suitable solvents can be used that are known to those skilled in the 
art. 
The mole ratio of oleoyl chloride to propoxylated sucrose can range between 
about 8.0 and about 8.8, preferably between about 8.2 and about 8.6. 
The oleoyl chloride solution is added dropwise to the stirred, heated 
Niax.RTM.solution under nitrogen, over a period of about 1.5 hours. The 
time for addition can vary between about 1 hour and about 3 hours. 
After completion of the addition, the reactants are heated to 55.degree. C. 
(131.degree. F.) and reacted for 20 hours. The reaction temperature can 
vary between about 45.degree. C. (113.degree. F.) and the solvent reflux 
temperature (about 59.degree. C. (138.degree. F.) in this example). The 
reaction time is between about 16 hours and about 48 hours, preferably 
between about 20 hours and about 26 hours. 
After the reaction is complete, the reactants are cooled to about room 
temperature and stirred under nitrogen for about 16 hours (can vary 
between about 1 hour and about 20 hours). 
The product is isolated by any suitable method known to the art. Example 1 
hereinbelow discloses details of the preferred method for isolating a 
propoxylated sucrose octaoleate according to the invention. 
D. Resistance of the Present Alkoxylated Sugar and Sugar Alcohol Polyesters 
to Hydrolysis 
The propoxylated sucrose polyester product of Example 1 hereinbelow is 
measured for resistance to hydrolysis by two techniques: (1) a 30-minute 
digest with commercial porcine lipase, and (2) a pH stat hydrolysis rate 
measurement with rat pancreatic juice. 
(1) Digest with Steapsin 
The initial screening of this product is performed with steapsin, a porcine 
pancreatic lipase, in a digest medium of Tris buffer, pH 8.0. The 
substrate (propoxylated sucrose polyester), medium, and enzyme are 
emulsified by vigorous shaking on a wrist-action shaker for thirty minutes 
at room temperature. The measurement of hydrolysis is by titration with a 
standardized base solution using phenophthalein indicator. The free fatty 
acid released by enzyme is the equivalent of the base consumed in the 
titration and is expressed as a percent of the total fatty acid initially 
present in the product. The data presented in Table I are the result of 
initial stability testing with steapsin. The data suggest that little or 
no hydrolysis occurs in the presence of the porcine lipase. (There is no 
titration for the presence of free acid in the samples prior to digestion 
by lipase, and the apparent low percent hydrolysis could be even lower if 
this assessment is made.) 
TABLE I 
__________________________________________________________________________ 
Percent Hydrolysis with Commerical Lipase 
M. W. 
Fat 
Fat F. A. 
KOH KOH F.F.A. 
% Hydrolysis 
Product 
(gm/mol) 
(mg) 
(umol) 
(umol) 
(ml) 
(umol) 
(umol) 
of Ester Bonds 
__________________________________________________________________________ 
Example 1 
3654 522 
143 -- 0.05 
5 5 0.3 
Crisco Oil 
885 654 
738 2216 
14.20 
1346 
1346 
60.7 
__________________________________________________________________________ 
(2) pH Stat Measurement with Pancreatic Juice 
The in vitro lipolysis of the product of Example 1 is examined using a pH 
Stat recording titrator. A nominal 1 gram of the product (substrate) is 
added to 70 ml of histidine buffer medium containing 1 ml of a 1% sodium 
taurocholate solution. The medium is emulsified in a 100 ml 4-neck 
roundbottom flask by vigorous shaking with a wrist-action shaker for 10 
minutes. The flask is then fitted with pH electrode, titrant delivery 
tube, and propeller stirrer. The reaction is initiated by delivery of 1.0 
ml of enzyme (bile-pancreatic combination fluid) into the stirred 
emulsion. The pH is maintained at 9.0 by the addition of 0.1 N KOH 
delivered from a Metrohm pH stat-titrator system. The linear portion of 
the plot resulting from added base versus time during the first 1-4 
minutes of the reaction is used to determine the rate of fatty acid 
production for the product. 
The digestibility of the product is shown in Table II. In contrast to the 
porcine lipase, the bile-pancreatic combination fluid contains nonspecific 
lipase which would hydrolyze both primary and secondary esters and, 
therefore, might potentially hydrolyze any ester bond in the product. 
Evidence for the activity of nonspecific lipase in the combination fluid 
is seen in the hydrolysis tracing of the product. The assessment of 
hydrolytic stability by pH-stat tracing essentially confirms the 
preliminary findings with porcine pancreatic lipase. 
TABLE II 
______________________________________ 
Rate of 
Hydrolysis 
Product Sample Wt. (gm) 
(ueq KOH/min) 
______________________________________ 
Example 1 1.0011 0.0 
______________________________________ 
E. Low Calorie Fat-Containing Food Compositions 
The alkoxylated sugar and sugar alcohol polyesters of the present invention 
can be used as partial or total replacements for normal triglyceride fats 
in any fat-containing food composition to provide low calorie benefits. 
The amount of the present compounds included in the fat will depend upon 
the food composition and the low calorie effect desired. In order to 
obtain a significant low calorie effect, it is necessary that at least 
about 10% of the fat in the food composition comprise the present 
compounds. On the other hand, very low calorie and thus highly desirable 
food compositions of the present invention are obtained when the fat 
comprises up to 100% of the present compounds. 
The compounds of the present invention are useful in a wide variety of food 
and beverage products. For example, the compounds can be used in the 
production of baked goods in any form, such as mixes, shelf-stable baked 
goods, and frozen baked goods. Possible applications include, but are not 
limited to, cakes, brownies, muffins, bar cookies, wafers, biscuits, 
pastries, pies, pie crusts, and cookies, including sandwich cookies and 
chocolate chip cookies, particularly the storage-stable dual-textured 
cookies described in U.S. Pat. No. 4,455,333 of Hong & Brabbs. The baked 
goods can contain fruit, cream, or other fillings. Other baked good uses 
include breads and rolls, crackers, pretzels, pancakes, waffles, ice cream 
cones and cups, yeast-raised baked goods, pizzas and pizza crusts, baked 
farinaceous snack foods and other baked salted snacks. 
In addition to their uses in baked goods, the present compounds can be used 
alone or in combination with other regular, reduced calorie or zero 
calorie fats to make shortening and oil products. The other fats can be 
synthetic or derived from animal or vegetable sources, or combinations of 
these. Shortening and oil products include, but are not limited to, 
shortenings, margarines, spreads, butter blends, lards, cooking and frying 
oils, salad oils, popcorn oils, salad dressings, mayonnaise, and other 
edible oils. The present compounds can be used to make foods that are 
fried in oil (e.g., Pringle's potato chips, corn chips, tortilla chips, 
other fried farinaceous snack foods, French fries, doughnuts, and fried 
chicken). 
Imitation dairy products can also be made (e.g., butter, ice cream and 
other fat-containing frozen desserts, yogurt, and cheeses, including 
natural cheeses, processed cheeses, cream cheese, cottage cheese, cheese 
foods and cheese spread, milk, cream, sour cream, butter milk, and coffee 
creamer). 
The present compounds are also useful for making meat products (e.g, 
hamburgers, hot dogs, frankfurters, wieners, sausages, bologna and other 
luncheon meats, canned meats, including pasta/meat products, stews, 
sandwich spreads, and canned fish), meat analogs, tofu, and various kinds 
of protein spreads. 
Sweet goods and confections can also be made (e.g., candies, chocolates, 
chocolate confections, frostings and icings, syrups, cream fillings, and 
fruit fillings), as well as nut butters and various kinds of soups, dips, 
sauces and gravies. 
The present compounds can also be fortified with vitamins and minerals, 
particularly the fat-soluble vitamins. The fat-soluble vitamins include 
vitamin A, vitamin D, vitamin E, and vitamin K. The amount of the 
fat-soluble vitamins employed herein to fortify the present compounds can 
vary. If desired, the compounds can be fortified with a recommended daily 
allowance (RDA), or increment or multiple of an RDA, of any of the 
fat-soluble vitamins or combinations thereof. 
The present compounds are particularly useful in combination with 
particular classes of food and beverage ingredients. For example, an extra 
calorie reduction benefit is achieved when the compounds are used with 
noncaloric or reduced calorie sweeteners alone or in combination with 
bulking agents. Noncaloric or reduced calorie sweeteners include, but are 
not limited to, aspartame; saccharin; alitame, thaumatin; 
dihydrochalcones; cyclamates; steviosides; glycyrrhizins, synthetic alkoxy 
aromatics, such as Dulcin and P-4000; sucrolose; suosan; miraculin; 
monellin; sorbitol; xylitol; talin; cyclohexylsulfamates; substituted 
imidazolines; synthetic sulfamic acids such as acesulfame, acesulfam-K and 
n-substituted sulfamic acids; oximes such as perilartine; rebaudioside-A; 
peptides such as aspartyl malonates and succanilic acids; dipeptides; 
amino acid based sweeteners such as gem-diaminoalkanes, meta-aminobenzoic 
acid, L-aminodicarboxylic acid alkanes, and amides of certain 
alpha-aminodicarboxylic acids and gem-diamines; and 
3-hydroxy-4-alkyloxyphenyl aliphatic carboxylates or heterocyclic aromatic 
carboxylates. 
The compounds of the present invention can be used in combination with 
other noncaloric or reduced calorie fats, such as sugar or sugar alcohol 
fatty acid polyesters, branched chain fatty acid triglycerides, 
triglycerol ethers, polycarboxylic acid esters, sucrose polyethers, 
neopentyl alcohol esters, silicone oils/siloxanes, and dicarboxylic acid 
esters. Other partial fat replacements useful in combination with the 
present compounds are medium chain triglycerides, highly esterified 
polyglycerol esters, acetin fats, plant sterol esters, polyoxyethylene 
esters, jojoba esters, mono/diglycerides of fatty acids, and 
mono/diglycerides of short-chain dibasic acids. 
Bulking or bodying agents are useful in combination with the present 
compounds in many foods or beverages. The bulking agents can be 
nondigestible carbohydrates, for example, polydextrose and cellulose or 
cellulose derivatives, such as carboyxmethylcellulose, 
carboxyethylcellulose, hydroxypropylcellulose, methylcellulose and 
microcrystalline cellulose. Other suitable bulking agents include gums 
(hydrocolloids), starches, dextrins, fermented whey, tofu, maltodextrins, 
polyols, including sugar alcohols, e.g., sorbitol and mannitol, and 
carbohydrates, e.g., lactose. 
Similarly, foods and beverages can be made that combine the present 
compounds with dietary fibers to achieve the combined benefits of each. By 
"dietary fiber" is meant complex carbohydrates resistant to digestion by 
mammalian enzymes, such as the carbohydrates found in plant cell walls and 
seaweed, and those produced by microbial fermentation. Examples of these 
complex carbohydrates are brans, celluloses, hemicelluloses, pectins, gums 
and mucilages, seaweed extract, and biosynthetic gums. Sources of the 
cellulosic fiber include vegetables, fruits, seeds, cereals, and man-made 
fibers (for example, by bacterial synthesis). Commercial fibers such as 
purified plant cellulose, or cellulose flour, can also be used. Naturally 
occurring fibers include fiber from whole citrus peel, citrus albedo, 
sugar beets, citrus pulp and vesicle solids, apples, apricots, and 
watermelon rinds. 
Many benefits are obtained from the use of the present compounds in foods 
and beverages, either when used alone or in combination with the 
ingredients discussed above. A primary benefit is the calorie reduction 
achieved when the present compounds are used as a total or partial fat 
replacement. This calorie reduction can be increased by using combinations 
of the present compounds with reduced calorie sweeteners, bulking agents, 
or other reduced calorie or noncaloric fats. Another benefit which follows 
from this use is a decrease in the total amount of triglyceride fats in 
the diet. 
This discussion of the uses, combinations, and benefits of the present 
compounds is not intended to be limiting or all-inclusive. It is 
contemplated that other similar uses and benefits can be found that will 
fall within the spirit and scope of this invention. 
The following example is intended only to further illustrate the invention 
and is not intended to limit the scope of the invention which is defined 
by the claims. 
EXAMPLE 1 
(a) Preparation of a fatty acid polyester of propoxylated sucrose 
A propoxylated sucrose polyester according to the invention is prepared as 
follows. The starting material is Niax.RTM. E-651 polyol, a sucrose which 
has been reacted with 14 moles of propylene oxide to form a propoxylated 
sucrose and which, therefore, has eight secondary hydroxyl groups 
available for reaction with fatty acid chlorides. Niax.RTM. E-651 (34.1 
g., 0.027 mole) (Union Carbide, Danbury, Conn.) is diluted in DMF (50 
ml)/pyridine (100 ml). This solution is charged to a 1 liter, 3-neck 
round-bottom flask equipped with a reflux condensor, 300 ml cylindrical 
pressure equalizing addition funnel, thermometer, dry N2 purge and 
magnetic stirrer. Oleoyl chloride (72.5 g., 0.24 mole) is diluted in 
methylene chloride (200 ml) and the solution placed in the funnel. The 
reactor's contents are warmed to 40.degree.-45.degree. C. 
(104.degree.-113.degree. F.) and the system purged with dry N.sub.2. The 
oleoyl chloride solution is added dropwise to the stirred contents of the 
reactor over 1.5 hours. A precipitate of pyridine hydrochloride forms 
halfway through the addition. After completion of the addition, the 
reactants are heated to 55.degree. C. and held at that temperature for 20 
hours. They are then cooled to room temperature and stirred under N.sub.2 
for an additional 16 hours. 
At this point the reaction mixture is transferred to a 2 liter separatory 
funnel and washed three times with water. The organic phase is then 
concentrated in a rotary flash evaporator until no additional solvent is 
removed. The crude product is diluted with methylene chloride and 
transferred to a separatory funnel. The product is washed three times with 
10% HCl. Emulsification of the organic and aqueous phases occurs and 
requires the addition of small amounts of brine to effect phase 
separations. The organic phase is then washed with Ca(OH).sub.2 in water. 
Insoluble calcium oleate salts are removed from the system by suction 
filtration through a packed Celite bed and the organic phase washed with 
neutral brine. 
The organic phase is then dried over MgSO.sub.4 and the desiccant removed 
by suction filtration. The product is isolated by concentrating it in a 
rotary flash evaporator at 70.degree. C. (158.degree. F.) until no 
additional solvent is removed. Yield of the product is 86.6%. 
The product is a transparent light amber oil with a mild odor reminiscent 
of leather. It has a low viscosity. 
(b) Food compositions accordinq to the present invention 
Low calorie fat-containing food compositions are prepared by using the 
propoxylated sucrose polyesters prepared as described in Example 1 in the 
following formulations: 
______________________________________ 
Ingredients % by weight 
______________________________________ 
Example I - Salad Oils 
(A) Refined, bleached, and lightly 
50 
hydrogenated soybean oil 
Propoxylated sucrose 
50 
polyesters 
100 
(B) Refined cottonseed oil 
90 
Propoxylated sucrose 
10 
polyesters 
100 
(C) Propoxylated sucrose 
100 
polyesters 
Example II - Plastic Shortening 
(A) Lightly hydrogenated soybean 
50 
oil (I.V. 107) 
Propoxylated sucrose 
40 
polyesters 
Tristearin (hardstock, I.V. 8) 
10 
100 
(B) 50/50 mixture of hardened 
40 
cottonseed oil and lard 
Monoglycerides of soybean oil 
10 
Propoxylated sucrose 
50 
polyesters 
100 
(C) Propoxylated sucrose 
100 
polyesters 
Example III - Prepared Cake Mix 
(A) Specific 
Cake flour 36 
Sugar 44 
Shortening (propoxylated 
13 
sucrose polyesters) 
Nonfat dried milk solids 
4 
Leavening 2 
Salt 1 
100 
(B) General 
Sugar 35-50 
Flour 25-50 
Shortening (propoxylated 
5-30 
sucrose polyesters) 
Leavening 1-4 
Cocoa 0-7 
Egg 0-5 
Milk solids 0-5 
Flavor 0-5 
100 
Example IV - Prepared Icing Mix 
Shortening (50/50 mixture of 
20 
conventional vegetable 
shortening and propoxylated 
sucrose polyesters) 
Salt 2 
Nonfat dry milk solid 
5 
Sugar 73 
100 
Example V - Mayonnaise 
Fat (75:25 blend of 75 
propoxylated sucrose 
polyesters and refined 
cottonseed oil) 
Vinegar 10 
Egg yolk 9 
Sugar 3 
Salt 1 
Mustard 1 
Flavor 1 
100 
Example VI - Salad Dressing 
Fat (propoxylated 50 
sucrose polyesters) 
Cornstarch 5 
Vinegar 10 
Water 35 
100 
Example VII - Margarine 
Oil (propoxylated 80 
sucrose polyesters) 
Milk solids 2 
Salt 2 
Monoglyceride 15 
Water 1 
100 
______________________________________ 
(c) Synthesis of the oleoyl chloride reactant 
Following is the preferred method for synthesizing the oleoyl chloride used 
in making the product of Example 1. 
Oleic acid (141 g, 0.50 mole) is dissolved in methanol (250 ml) in a 2 
liter Erlenmeyer flask and potassium hydroxide pellets (28.2 g, 0.50 mole) 
added. The mixture is then stirred while the pellets gradually dissolve. 
After four to five hours, reagent grade acetone (1 liter) is slowly added 
to the solution and a white precipitate formed. The flask is then 
stoppered and stored in a freezer overnight. The following day the 
potassium oleate precipitate is collected by suction filtration and washed 
on the filter with additional acetone. The potassium oleate is then dried 
at first in a forced air oven at 50.degree. C. (122.degree. F.) and 
finally in a vacuum oven at 45.degree. C. (113.degree. F.). Yield of 
potassium oleate is in the 80 to 90 percent range, about 140 g per batch. 
A 5 liter, three-neck round bottom flask is equipped with a refluxing 
condenser, a magnetic stirrer, a 250 ml cylindrical funnel, and an argon 
purge. The flask is charged with dry potassium oleate (230 g, 0.72 mole) 
slurried in 1 to methylene chloride - hexane (2.5 liters) and a few 
crystals of KCl added to the flask. The flask is then purged with argon 
gas and kept under a positive head of argon. The entire contents of an 
ampule of oxalyl chloride (100 g, 0.79 mole) is diluted with methylene 
chloride (100 ml) and poured into the cylindrical funnel. The oxalyl 
chloride solution is added dropwise to the slurry with gentle stirring 
over a 2 to 3 hour period with substantial evolution of CO.sub.2 and CO 
occurring. During the addition the potassium oleate gradually disappears 
and is replaced by a finer precipitate of KCl. The reaction miXlure is 
allowed to stand under argon with no further agitation overnight. The 
following day the KCl precipitate is removed from the product solution by 
suction filtration through a bed of Celite (diatomaceous earth). The 
filtered solution is then concentrated by rotary flash evaporation until 
no additional solvent is removed from the product. The product is stored 
in sealed bottles under argon until used. The oleoyl chloride prepared is 
a pale yellow oil with a pungent odor. Yield of this reaction is about 90 
percent. Confirmation of the product,s identity is made by infrared 
spectroscopy.