CA1284337C - Synthetic cooking oils containing dicarboxylic acid esters - Google Patents
Synthetic cooking oils containing dicarboxylic acid estersInfo
- Publication number
- CA1284337C CA1284337C CA000501295A CA501295A CA1284337C CA 1284337 C CA1284337 C CA 1284337C CA 000501295 A CA000501295 A CA 000501295A CA 501295 A CA501295 A CA 501295A CA 1284337 C CA1284337 C CA 1284337C
- Authority
- CA
- Canada
- Prior art keywords
- diester
- edible oil
- radical
- synthetic edible
- carbon atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- Coloring Foods And Improving Nutritive Qualities (AREA)
- Edible Oils And Fats (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Diesters of the formula
Diesters of the formula
Description
3~7 91~-1091A SYNTEIETIC COOKING OILS CONTAINING
GG:570 DICARBOXYLIC ACID ESTERS
FIELD OF THE INVE~TION
The present invention relates to the synthesis and use o~ synthetic oils as substitutes for animal and vegetable fats and oils in the preparation of foods for human and animal consumption.
BACKGROUND OF THE INVE~TION
Lipids (fats and oils) constitute between 30 and 40%
of the caloric intake of the average American diet.
Dietary fat, consisting of triglycerides, is digested to free fatty acids and monoglycerides, primarily in the small intestine. The -lipase steapsin cleaves the glycerol esters at the 1- and 3- positions. Fatty acids of 6 to 10 carbons and unsaturated fatty acids are rapidly absorbed, while those of 12 to 18 carbons are absorbed more slowly. Absorption of the -monoglycerides by the mucosa of the small intestine results in a final digestion and absorption of up to 95% of the total dietary fat. Since fats yield about twice the energy per gram of either carbohydrates or proteins, substitution of a non-digestible material for a portion of the normal dietary fat offers a painless and effective method for control of obesity, hypertension, and other diseases associated with excessive caloric intake.
There is considerable evidence that steapsin is an enzyme which is specific for esters of 1, 3-diols and 3Q glycerol. U.S. Patent No. 2,962,419 to ~inich describes ln vitro tests of pentaerythretol tetracaprylate to demonstrate that there is no hydrolysis of the pentaerythritol ester by pancreatic lipase (steapsin) and a greatly diminished total serum lipid concentration when the substance was used in place of fat in a typical rat ~ ~:
., .
diet. Canadian Patent No. 1,106,681 to ~rrOst describes the feeding of dialkyl glycerol esters to rats, concluding that the esters were generally non-digestible, and tests of sucrose polyester in obese human volunteers showed decreased total plasma cholesterol and plaslna triglycerides (Glueck et al., Am. J. Cli. Nutri., 35, 1352 (1982)). U.S. Patent No. 3,600,186 to Mattson et al. describe the use of fatty acid ester compounds having at least 4 fatty acid ester groups for use as triglyceride fat substitutes.
Esters of malonic acid and dialkyl malonic acid, and low molecular weight alcohols are known but are unsuitable for use as vegetable oil substitutes due to their low boiling points.
There remains a need for stable synthetic oils which are not readily digestible in mammals, and which are suitable for use in the production of low calorie fried and baked products containing starches, and in other foods such as oleomargarine, salad oil and other foods 2~ normally containiny vegetable oils.
SUMMARY OF THE INVENTION
The invention provides esters of the formula O
C=O--X
Y---O--C
O
wherein R1 and R2 are hydrogen or alkyl radicals containing from 1 to about 20 carbon atoms, and X and Y
are alkyl, alkenyl or dienyl radicals containing from about 12 to about 18 carbon atoms. These materials are synthetic oils and low melting solids which are hydrolyzed slowly or not at all/ by pancreatic lipase.
Food products made with or fried in these synthetic oils contain less metabolizable lipids and are, therefore, lower in available calories, making them suitable for use by persons with weight or some lipid control difficulties.
DETAILED DESCRIPTION OF THE INVENTION
-The synthetic edible oils of the present invention are represented by the formula:
o Il C - O - X
Y--~C
o wherein Rl and R~, which may be the same or different, are hydrogen or alkyl radicals ot from 1 to about 20 carbon atoms, e.g., methyl, ethyl, nexadecyl, eicosyl, and the like; and X and Y, which may be the same or different, are alkyl, alkenyl or dienyl radicals of from about 1~ to about 18 carbon atoms, e.g., dodecyl, octadecyl, dodecenyl, oleyl, linoleyl, and the like.
~ ~L~
In preferred compounds, at least one of the R groups is an alkyl of from 1 to about 20 carbon atoms, the other R
group being hydrogen or a similar alkyl. In particularly preferred compounds, one of the R groups is hydrogen and the other is an alkyl of about 16 carbon atoms, or both R
groups are alkyls of about 16 carbon atoms.
The radicals X and ~ are preferably alkyl of from about 14 to about 18 carbon atoms, or alkenyls or dienyls of about 18 carbon atoms.
Particularly preferred compounds are dioleyl hexade-cylmalonate and dioleyl dihexadecylmalonate.
The compounds of this invention are synthetic organic compounds which display the physical properties of animal fats and vegetable oils. They are liquid or solid at room temperature, depending upon molecular weight and structure, and oils at normal cooking temperatures. Unlike naturally-occurring fats and oils, which are triglycerides (fatty acid esters of glycerol) the products of this invention are fatty alcohol derivatives of malonic acid, and mono- and dialkyl malonic acid. Unlike triglycerides, these com-pounds resist hydrolysis by pancreatic lipase and other components of the digestive juices present in the stomach and small intestine. As a result, most of the materiaI is not absorbed by the small intestine.
Examples of fatty alcohols suitable for the practice of this invention include oleyl, myristic, linoleic, pal-mitic and stearic ~lcohols, with oleyl alcohol being particularly preferred. They are readily available commercially, and readily synthesized by reduction of the corresponding fatty acid obtained by the saponification of fats and oils. Suitable acids include maIonic acid, monoalkyl and dialkyl malonic acid, such as hexadecyl-malonic acid and dihexadecylmalonic acid. Both the .
;
,:
~ ~ ., ' .' .
. :
' '' ~ ~ ' ' '. ' "
pure, symmetric diesters and mlxed esters are suitable, analogous to the mixed esters in naturally-occurring fats and oils.
rhe synthesis of the compounds of this invention may be accomplished by several pathways. For example, certain compounds of the invention may be prepared by reacting a malonyl dihalide with a fatty alcohol or a mixture of fatty alcohols. If desired, the product may then be reacted with an alkyl halide, or a mixture of alkyl halides, in a basic solution to produce a product of higher molecular weight with a correspondingly higher melting point and boiling point.
Impurities may be removed from the esters formed by the above procedures by vacuum distillation or silica gel chromatography using conventional equipment and techniques familiar to those experienced in the chemical arts.
The lower molecular weight compounds of the present invention are suitable as substitutes for natural oils in spreads such as mayonnaise and margarine, and other food products which are not subjected to high temperatures for long periods of time. Higher molecular weight compounds are preferred for use as synthetic frying oils.
The synthetic oils of the present invention may also comprise mi~tures of the disclosed compounds.
particularly preferred synthetic oils of the present invention have a melting point below about 10C, a boiling point above about 230C, are absorbed by the small intestine of a mammal at a substantially lower rate than corn oil, and/or provide substantially fewer calories than corn oil when consumed by a mammal.
Food products fried in synthetic oils of the present invention have a lower metabolic fat content than a similar product cooked in animal Eat or vegetable oil.
Similarly, food products in which their normal content of animal fat or vegetable oil has been partially or completely substituted by the synthetic oils o~ this invention have a lower metabolic fat content than similar products not containing synthetic oil.
The invention is further illustrated by the following example, which is not intended to be limiting.
Preparation of Dioleyl Hexadecylmalonate and Dioleyl Dihexadecylmalonate 1~ Three molar equivalents of l-bromohexadecane (available from Fluka Chemical Corporation), one molar equivalent of dioleyl malonate (prepared by the reaction of malonyl dichloride (Aldrich) with oleyl alcohol (Aldrich)), 0.1 molar equivalent of tetra-n-butylammonium hydroxide (40% solution in water (Aldrich)), and 2-3 molar equivalents of potassium hydroxide (50% solution in water) were combined in a flask with a small amount of water and stirred 2-~ hours at room temperature (20-25C).
Stirring for two hours with two molar equivalents of potassium hydroxide resulted in a mixture containing ap-proximately 67% dioleyl hexadecylmalonate and 33% dioleyl dihexadecylmalonate. Stirring for four hours with three molar equivalents potassium hydroxide gave a higher pro-portion (67%) of dioleyl dihexadecylmalonate. The two malonic esters were purified by removal of the aqueous phase by extraction with water, vacuum distillation to remove unreacted bromohexadecane and oleyl alcohol bypro-duct, and silica gel chromatography using petroleum ether.
The dioleyl dihexadecylmalonate was distinguished by its higher melting point (36-37C), quaternary carbon nmr signal at 56 ppm and molecular ion (1054). The dioleyl ., .
, ~ ' ` ' :' ' ' .
hexadecylmalonate had a melting point of 28-29C, tertiary carbon nmr signal at 52 ppm, and molecular ion (829).
. .
:
.
GG:570 DICARBOXYLIC ACID ESTERS
FIELD OF THE INVE~TION
The present invention relates to the synthesis and use o~ synthetic oils as substitutes for animal and vegetable fats and oils in the preparation of foods for human and animal consumption.
BACKGROUND OF THE INVE~TION
Lipids (fats and oils) constitute between 30 and 40%
of the caloric intake of the average American diet.
Dietary fat, consisting of triglycerides, is digested to free fatty acids and monoglycerides, primarily in the small intestine. The -lipase steapsin cleaves the glycerol esters at the 1- and 3- positions. Fatty acids of 6 to 10 carbons and unsaturated fatty acids are rapidly absorbed, while those of 12 to 18 carbons are absorbed more slowly. Absorption of the -monoglycerides by the mucosa of the small intestine results in a final digestion and absorption of up to 95% of the total dietary fat. Since fats yield about twice the energy per gram of either carbohydrates or proteins, substitution of a non-digestible material for a portion of the normal dietary fat offers a painless and effective method for control of obesity, hypertension, and other diseases associated with excessive caloric intake.
There is considerable evidence that steapsin is an enzyme which is specific for esters of 1, 3-diols and 3Q glycerol. U.S. Patent No. 2,962,419 to ~inich describes ln vitro tests of pentaerythretol tetracaprylate to demonstrate that there is no hydrolysis of the pentaerythritol ester by pancreatic lipase (steapsin) and a greatly diminished total serum lipid concentration when the substance was used in place of fat in a typical rat ~ ~:
., .
diet. Canadian Patent No. 1,106,681 to ~rrOst describes the feeding of dialkyl glycerol esters to rats, concluding that the esters were generally non-digestible, and tests of sucrose polyester in obese human volunteers showed decreased total plasma cholesterol and plaslna triglycerides (Glueck et al., Am. J. Cli. Nutri., 35, 1352 (1982)). U.S. Patent No. 3,600,186 to Mattson et al. describe the use of fatty acid ester compounds having at least 4 fatty acid ester groups for use as triglyceride fat substitutes.
Esters of malonic acid and dialkyl malonic acid, and low molecular weight alcohols are known but are unsuitable for use as vegetable oil substitutes due to their low boiling points.
There remains a need for stable synthetic oils which are not readily digestible in mammals, and which are suitable for use in the production of low calorie fried and baked products containing starches, and in other foods such as oleomargarine, salad oil and other foods 2~ normally containiny vegetable oils.
SUMMARY OF THE INVENTION
The invention provides esters of the formula O
C=O--X
Y---O--C
O
wherein R1 and R2 are hydrogen or alkyl radicals containing from 1 to about 20 carbon atoms, and X and Y
are alkyl, alkenyl or dienyl radicals containing from about 12 to about 18 carbon atoms. These materials are synthetic oils and low melting solids which are hydrolyzed slowly or not at all/ by pancreatic lipase.
Food products made with or fried in these synthetic oils contain less metabolizable lipids and are, therefore, lower in available calories, making them suitable for use by persons with weight or some lipid control difficulties.
DETAILED DESCRIPTION OF THE INVENTION
-The synthetic edible oils of the present invention are represented by the formula:
o Il C - O - X
Y--~C
o wherein Rl and R~, which may be the same or different, are hydrogen or alkyl radicals ot from 1 to about 20 carbon atoms, e.g., methyl, ethyl, nexadecyl, eicosyl, and the like; and X and Y, which may be the same or different, are alkyl, alkenyl or dienyl radicals of from about 1~ to about 18 carbon atoms, e.g., dodecyl, octadecyl, dodecenyl, oleyl, linoleyl, and the like.
~ ~L~
In preferred compounds, at least one of the R groups is an alkyl of from 1 to about 20 carbon atoms, the other R
group being hydrogen or a similar alkyl. In particularly preferred compounds, one of the R groups is hydrogen and the other is an alkyl of about 16 carbon atoms, or both R
groups are alkyls of about 16 carbon atoms.
The radicals X and ~ are preferably alkyl of from about 14 to about 18 carbon atoms, or alkenyls or dienyls of about 18 carbon atoms.
Particularly preferred compounds are dioleyl hexade-cylmalonate and dioleyl dihexadecylmalonate.
The compounds of this invention are synthetic organic compounds which display the physical properties of animal fats and vegetable oils. They are liquid or solid at room temperature, depending upon molecular weight and structure, and oils at normal cooking temperatures. Unlike naturally-occurring fats and oils, which are triglycerides (fatty acid esters of glycerol) the products of this invention are fatty alcohol derivatives of malonic acid, and mono- and dialkyl malonic acid. Unlike triglycerides, these com-pounds resist hydrolysis by pancreatic lipase and other components of the digestive juices present in the stomach and small intestine. As a result, most of the materiaI is not absorbed by the small intestine.
Examples of fatty alcohols suitable for the practice of this invention include oleyl, myristic, linoleic, pal-mitic and stearic ~lcohols, with oleyl alcohol being particularly preferred. They are readily available commercially, and readily synthesized by reduction of the corresponding fatty acid obtained by the saponification of fats and oils. Suitable acids include maIonic acid, monoalkyl and dialkyl malonic acid, such as hexadecyl-malonic acid and dihexadecylmalonic acid. Both the .
;
,:
~ ~ ., ' .' .
. :
' '' ~ ~ ' ' '. ' "
pure, symmetric diesters and mlxed esters are suitable, analogous to the mixed esters in naturally-occurring fats and oils.
rhe synthesis of the compounds of this invention may be accomplished by several pathways. For example, certain compounds of the invention may be prepared by reacting a malonyl dihalide with a fatty alcohol or a mixture of fatty alcohols. If desired, the product may then be reacted with an alkyl halide, or a mixture of alkyl halides, in a basic solution to produce a product of higher molecular weight with a correspondingly higher melting point and boiling point.
Impurities may be removed from the esters formed by the above procedures by vacuum distillation or silica gel chromatography using conventional equipment and techniques familiar to those experienced in the chemical arts.
The lower molecular weight compounds of the present invention are suitable as substitutes for natural oils in spreads such as mayonnaise and margarine, and other food products which are not subjected to high temperatures for long periods of time. Higher molecular weight compounds are preferred for use as synthetic frying oils.
The synthetic oils of the present invention may also comprise mi~tures of the disclosed compounds.
particularly preferred synthetic oils of the present invention have a melting point below about 10C, a boiling point above about 230C, are absorbed by the small intestine of a mammal at a substantially lower rate than corn oil, and/or provide substantially fewer calories than corn oil when consumed by a mammal.
Food products fried in synthetic oils of the present invention have a lower metabolic fat content than a similar product cooked in animal Eat or vegetable oil.
Similarly, food products in which their normal content of animal fat or vegetable oil has been partially or completely substituted by the synthetic oils o~ this invention have a lower metabolic fat content than similar products not containing synthetic oil.
The invention is further illustrated by the following example, which is not intended to be limiting.
Preparation of Dioleyl Hexadecylmalonate and Dioleyl Dihexadecylmalonate 1~ Three molar equivalents of l-bromohexadecane (available from Fluka Chemical Corporation), one molar equivalent of dioleyl malonate (prepared by the reaction of malonyl dichloride (Aldrich) with oleyl alcohol (Aldrich)), 0.1 molar equivalent of tetra-n-butylammonium hydroxide (40% solution in water (Aldrich)), and 2-3 molar equivalents of potassium hydroxide (50% solution in water) were combined in a flask with a small amount of water and stirred 2-~ hours at room temperature (20-25C).
Stirring for two hours with two molar equivalents of potassium hydroxide resulted in a mixture containing ap-proximately 67% dioleyl hexadecylmalonate and 33% dioleyl dihexadecylmalonate. Stirring for four hours with three molar equivalents potassium hydroxide gave a higher pro-portion (67%) of dioleyl dihexadecylmalonate. The two malonic esters were purified by removal of the aqueous phase by extraction with water, vacuum distillation to remove unreacted bromohexadecane and oleyl alcohol bypro-duct, and silica gel chromatography using petroleum ether.
The dioleyl dihexadecylmalonate was distinguished by its higher melting point (36-37C), quaternary carbon nmr signal at 56 ppm and molecular ion (1054). The dioleyl ., .
, ~ ' ` ' :' ' ' .
hexadecylmalonate had a melting point of 28-29C, tertiary carbon nmr signal at 52 ppm, and molecular ion (829).
. .
:
.
Claims (33)
1. A diester of the formula:
wherein R1 and R2, which may be the same or different, each one is hydrogen or an alkyl radical of from 1 to 20 carbon atoms, with the proviso that at least one of said R1 and R2 is an alkyl radical of from 1 to 20 carbon atoms;
X is an alkyl radical of from 12 to 18 carbon atoms or an oleyl radical or a linoleyl radical; and Y is an oleyl radical or a linoleyl radical.
wherein R1 and R2, which may be the same or different, each one is hydrogen or an alkyl radical of from 1 to 20 carbon atoms, with the proviso that at least one of said R1 and R2 is an alkyl radical of from 1 to 20 carbon atoms;
X is an alkyl radical of from 12 to 18 carbon atoms or an oleyl radical or a linoleyl radical; and Y is an oleyl radical or a linoleyl radical.
2. A diester as claimed in claim 1, wherein one of R1 and R2 is hydrogen and the other is an alkyl rad-ical of 16 carbon atoms.
3. A diester as claimed in claim 1, wherein each one of R1 and R2 is an alkyl radical of 16 carbon atoms.
4. A diester as claimed in claim 1, wherein each one of X and Y is an oleyl radical.
5. A diester as claimed in claim 1, wherein each one of X and Y is a linoleyl radical.
6. A diester of claim 1, wherein one of R1 and R2 is hydrogen and the other is an alkyl radical of 16 car-bon atoms and each one of X and Y is an oleyl radical.
7. A diester as claimed in claim 1, wherein each one of R1 and R2 is an alkyl radical of 16 carbon atoms and each one of X and Y is an oleyl radical.
8. A diester of claim 1 wherein each one of R1 and R2 is an alkyl radical of 16 carbon atoms and each one of X and Y is a linoleyl radical.
9. The diester which is dioleyl hexadecylmalo-nate.
10. The diester which is dioleyl dihexadecylmalo-nate.
11. A synthetic edible oil comprising at least one diester of the formula:
wherein R1 and R2, which may be the same or different, each one is hydrogen or an alkyl radical of from 1 to 20 carbon atoms, with the proviso that at least one of said R1 and R2 is an alkyl radical of from 1 to 20 carbon atoms;
X is an alkyl, alkenyl or alkadienyl radical of from 12 to 18 carbon atoms; and Y is an alkenyl or alkadienyl radical of from 12 to 18 carbon atoms.
wherein R1 and R2, which may be the same or different, each one is hydrogen or an alkyl radical of from 1 to 20 carbon atoms, with the proviso that at least one of said R1 and R2 is an alkyl radical of from 1 to 20 carbon atoms;
X is an alkyl, alkenyl or alkadienyl radical of from 12 to 18 carbon atoms; and Y is an alkenyl or alkadienyl radical of from 12 to 18 carbon atoms.
12. A synthetic edible oil comprising a diester of claim 1.
13. A synthetic edible oil comprising a diester of claim 2.
14. A synthetic edible oil comprising a diester of claim 3.
15. A synthetic edible oil comprising a diester of claim 4.
16. A synthetic edible oil comprising a diester of claim 5.
17. A synthetic edible oil comprising a diester of claim 6.
18. A synthetic edible oil comprising a diester of claim 7.
19. A synthetic edible oil comprising a diester of claim 8.
20. A synthetic edible oil comprising a diester of claim 9.
21. A synthetic edible oil comprising a diester of claim 10.
22. A synthetic edible oil comprising a mixture of dioleyl hexadecylmalonate and dioleyl dihexadecylmalo-nate.
23. A synthetic edible oil of claim 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22, having a melting point below about 10°C and a boiling point above about 230°C.
24. A synthetic edible oil of claim 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22, which is capable of being adsorbed by the small intestine of a mammal at a substantially lower rate than corn oil.
25. A synthetic edible oil of claim 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22, which is capable of providing substantially fewer calories than corn oil when consumed by a mammal.
26. A fried food product when fried in a synthetic edible oil of claim 11.
27. A food product of claim 26 having a lower metabolic fat content than a corresponding product cooked in an animal fat or a vegetable oil.
28. A food product of claim 26 when fried in dioleyl hexadecylmalonate.
29. A food product of claim 26 when fried in dioleyl dihexadecylmalonate.
30. A food product when fried in a synthetic edible oil comprising a mixture of dioleyl hexadecyl-malonate and dioleyl dihexadecylmalonate.
31. A food product containing a synthetic edible oil of claim 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22.
32. A food product when fried in a synthetic edible oil of claim 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22.
33. A method of frying food comprising heating a synthetic edible oil of claim 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22 to frying temperature and contacting an article of food with said synthetic edible oil for a time sufficient to fry said food.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000501295A CA1284337C (en) | 1986-02-06 | 1986-02-06 | Synthetic cooking oils containing dicarboxylic acid esters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000501295A CA1284337C (en) | 1986-02-06 | 1986-02-06 | Synthetic cooking oils containing dicarboxylic acid esters |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1284337C true CA1284337C (en) | 1991-05-21 |
Family
ID=4132426
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000501295A Expired - Lifetime CA1284337C (en) | 1986-02-06 | 1986-02-06 | Synthetic cooking oils containing dicarboxylic acid esters |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1284337C (en) |
-
1986
- 1986-02-06 CA CA000501295A patent/CA1284337C/en not_active Expired - Lifetime
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed | ||
| MKLA | Lapsed |
Effective date: 19931123 |