AU594040B2 - Synthetic cooking oils containing dicarboxylic acid esters - Google Patents

Description

i 1I1-:~II--~--CL~Yrm-_i~ 594040 T R A L I A C O M M O N W E A L TH F A U S PATENT ACT 1952 COMPLETE SPECIFICATION (Original) FOR OFFICE USE

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Application Number: 6 3 7 Lodged: Complete Specification Lodged: Accepted: Published: Priority: Thi Related Art: arte Sect $Ci lass Int. Class 0 or o o 0 C 0 C 00 I C 0 1 C 0 C 00 CC 0 C 0 C 0 CC 004 E Name of Applicant: c t Address of Applicant: FRITO-LAY, INC.

7701 Carpenter Road, Plano, Texas 75024-4099 UNITED STATES OF AMERICA 0 0 Actual Inventor(s): John G. FULCHER 0 c o tC SAddress for Service: DAVIES COLLISON, Patent Attorneys, 1 Little Collins Street, Melbourne, 3000.

Complete Specification for the invention entitled:.

"SYNTHETIC COOKING OILS CONTAINING DICARBOXYLIC ACID ESTERS" The following statement is a full description of this invention, including the best method of performing it known to us r- i To: THE COM M ISSIONER OF PATENTS (a member of the firm of DAVIES APPICATFON ACCEPTED AND AMENDMENTS COLLISON for and on behalf of the Applicant).

ALLOW ED Davies Collison, Melbourne and Canberra.

1A 914-1091A SYNTHETIC COQKING OILS CONTAINING GG:570 DICARBOXYLIC ACID ESTERS FIELD OF THE INVENTION The present invention relates to the synthesis and use of synthetic oils as substitutes for animal and vegetable fats and oils in the preparation of foods for human and animal consumption.

BACKGROUND OF THE INVENTION Lipids (fats and oils) constitute between 30 and of the caloric intake of the average American diet.

Dietary fat, consisting of triglycerides, is digested to o 00 free fatty acids and monoglycerides, primarily in the o000 o 15 small intestine. The -lipase steapsin cleaves the 0 0 0o o glycerol esters at the 1- and 3- positions. Fatty acids 00C 0 00 0 0of 6 to 10 carbons and unsaturated fatty acids are 0 o rapidly absorbed, while those of 12 to 18 carbons are a 00 0 o°o absorbed more slowly. Absorption of the -monoglycerides g0o 0 by the mucosa of the small intestine results in a final digestion and absorption of up to 95% of the total 0 00 00 0 Soeo dietary fat. Since fats yield about twice the energy per a 00 0oo gram of either carbohydrates or proteins, substitution of a non-digestible material for a portion of the normal 00 *0 25 dietary fat offers a painless and effective method for control of obesity, hypertension, and other diseases associated with excessive caloric intake.

696oo o* There is considerable evidence that steapsin is an *00"00 enzyme which is specific for esters of 1, 3-diols and glycerol. U.S. Patent No. 2,962,419 to Minich describes in 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

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d 11(l I I- (i .l l A JI -it I Signature(s) of declarant(s).

To: The Commissioner of Patents, Australia 2 diet. Canadian Patent No. 1,106,681 to Trost 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 plasma triglycerides (Glueck et al., Am. J. Cli. Nutri., 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 triglyceriae fat substitutes.

Esters of malonic acid and dialkyl malonic acid, and low molecular weight alcohols are known but are o c unsuitable for use as vegetable oil substitutes due to oo their low boiling points.

o ,c 15 There remains a need for stable synthetic oils which a 0 t o are not readily digestible in mammals, and which are oo et o 0 suitable for use in the production of low calorie fried 0 t oa t and baked products containing starches, and in other foods such as oleomargarine, salad oil and other foods a o 20 normally containing vegetable oils.

0 0 t Do t o a a SUMMARY OF THE INVENTION S, Te in ntion provid c torc of 4the formu la o0 v 0 a R C- S1-C--R2 SY--0- L. 3 1 The invention provides a synthetic edible oil 2 comprising one or more compounds of the formula 3 4

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RI--C--R2

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0 0 00 00 0000 0 00 0 0 0 00 00 00 0 S 0o 00 00 0 0 0 0 000 000 0 0000 00 0 00 0 0 00 0 000000 0 0 0 000000 0 0 0000 0 0 0 00 0 00 0 0 0 0 0 00 wherein R 1 and R 2 which may be the same or different, are hydrogen or alkyl of from 1 to 20 carbon atoms, with the proviso that at least one of the R groups, R 1 or R 2 is an alkyl of from 1 to 20 carbon atoms; and X and Y, which may be the same or different, are alkyl, alkenyl or alkadienyl radicals of from 12 to 18 carbon atoms.

DETAILED DESCRIPTION OF THE INVENTION Examples of R 1 and R 2 which may be the same or different, are alkyl radicals of from 1 to 20 carbon atoms, methyl, ethyl, hexadecyl, eicosyl, and the like; and X and Y, which may be the same or different, are alkyl, alkenyl or alkadienyl radicals of from 12 to 18 carbon atoms, dodecyl, octadecyl, dodecenyl, oleyl, linoleyl, and the like.

891128.csdat.066.bernard.1,11 4 n przicfrroc omonpounds, -a -lea'Ct noe-4- fTeRP.-roups i a1 a3lk'i ;oF frIom 1 to about 20 -carbon- atomc the other group bein ihydrog-n or a simi Jlar- li'l 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 Y are preferably alkyls of from about 14 to about 18 carbon atoms, or alkenyls or dienyls of about 1d carbon atoms.

Particularly preferred compounds are hexadecyl dioleylmalonate and dihexadecyl dioleylmalonate.

g The compounds of this invention are synthetic oo organic compounds which display the physical properties 0 0 o et 15 of animal fats and vegetable oils. They are liquid or 0 solid at room temperature, depending upon molecular 00 to o weight and structure, and oils at normal cooking 0 at 0o? f temperatures. Unlike naturally-occurring fats and oils, which are triglycerides (fatty acid esters of glycerol) the products of this invention are fatty alcohol o"o derivatives of malonic acid, and mono- and dialkyl o or s0o 0 malonic acid. Unlike triglycerides, these compounds 0n resist hydrolysis by pancreatic lipase and other 0 components of the digestive juices present in the stomach and small intestine. As a result, most of the material is not absorbed by the small intestine.

060600 O Examples of fatty alcohols suitable for the practice of this invention include oleyl, myristic, linoleic, palmitic and stearic alcohols, 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 malonic acid, monoalkyl and dialkyl malonic acid, such as hexadecyl malonic acid and dihexadecyl malonic acid. Both the _~_1111~_ pure, symmetric diesters and mixed esters are suitable, analogous to the mixed esters in naturally-occurring fats and oils.

The 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. It 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.

0 o0 t Impurities may be removed from the esters formed by 00ooC 0o the above procedures by vacuum distillation or silica gel c 04 15 chromatography using conventional equipment and 0 techniques familiar to those experienced in the cnemical 0. 03 o a arts.

o 00 0o• t The lower molecular weight compounds of the present invention are suitable as substitutes for natural oils in 00 20 spreads such as mayonnaise and margarine, and other food ooo0 products which are not subjected to high temperatures for 0 06 0 0 0 long periods of time. Higher molecular weight compounds S are preferred for use as syntnetic frying oils.

G The synthetic oils of the present invention may also comprise mixtures of the disclosed compounds.

particularly preferred synthetic oils of the present 6 invention have a melting point below about 10°C, a 0 So 1 oboiling point above about 230°C, 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 fat or vegetable oil.

Similarly, food products in which their normal content of 6 animal Eat or vegetable oil has been partially or completely substituted by the synthetic oils of this invention nave 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.

EXAMPLE 1 Preparation of Hexadecyl Dioleylmalonate and Dihexadecyl Dioleylmalonate Three molar equivalents of 1-bromohexadecane (available from Fluka Chemical Corporation), one molar 0o o equivalent of dioleylmalonate (prepared by the reaction 000 0°o 15 of malonyl dichloride (Aldrich) with oleyl alcohol o000 o (Aldrich)), 0.1 molar equivalent of tetra-n-butylammonium 0 o o 0 o00 o hydroxide (40% solution in water (Aldrich)), and 2-3 a molar equivalents of potassium nydroxide (50% solution in 0 00 o00 o water) were combined in a flask with a small amount of water and stirred 2-4 hours at room temperature a 00 250C).

0.0 Stirring for two hours with two molar equivalents of 0 0 0 S6o potassium hydroxide resulted in a mixture containing o a approximately 67% hexadecyl dioleylmalonate and 33% dihexadecyl dioleylmalonate. Stirring for four hours with three molar equivalents potassium hydroxide gave a o higher proportion of dihexadecyl dioleylmalonate.

a 0 o The two malonic esters were purified by removal of the 006000 0 0 aqueous phase by extraction with water, vacuum distillation to remove unreacted bromohexadecane and oleyl alcohol byproduct, and silica gel chromatography using petroleum ether.

The dihexadecyl dioleylmalonate was distinguished by its higher melting point (36-37 0 quaternary carbon nmr signal at 56 ppm and molecular ion (1054). The hexadecyl iLi t 7 dioleylinalonate had a melting point of 28-29'C, tertiary carbon nrnr signal at 52 ppm, and molecular ion (829).

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00 004 00 00 t~ 0 0 0 000 00 0 0 00 a o e0 00 0 O 00 0 0 .3 The invention provides a synthetic edible oil comprising one or more compounds of the formula R1--C-R 2

Y--O-C

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0 o *4: 0 0 0 O 0 00 00 00 0 0 0 f 0 4( 00 0 0 6 0 0 0 0 O O0 0 0 0 e0 o wherein R 1 and R 2 which may be the same or different, are hydrogen or alkyl of from 1 to 20 carbon atoms, with the proviso that at least one of the R groups, R 1 or R 2 is an alkyl of from 1 to 20 carbon atoms; and X and Y, which may be the same or different, are alkyl, alkenyl or alkadienyl radicals of from 12 to 18 carbon atoms.

DETAILED DESCRIPTION OF THE INVENTION Examples of R 1 and R 2 which may be the same or different, are alkyl radicals of from 1 to 20 carbon atoms, methyl, ethyl, hexadecyl, eicosyl, and the like; and X and Y, which may be the same or different, are alkyl, alkenyl or alkadienyl radicals of from 12 to 18 carbon atoms, dodecyl, octadecyl, dodecenyl, oleyl, linoleyl, and the like.

0 0 0 00 0 00 0 1128.c- dat.066.bernard.1,11

Claims (15)

1. 5. A synthetic edible oil comprising the diester of claim 35 oil. 36 4, wherein one of the R groups, R 1 and R 2 is hydrogen, and 36 37 the other of the R groups, R 1 and R 2 is an alkyl of 16 37 17. Th x carbon atoms. dioleyl 1128c-sdat.a66bernard.18 891128, csda 9
2. 6. A synthetic edible oil comprising the diester 4, wherein R 1 and R 2 are alkyls of 16 carbon atoms.
3. 7. A synthetic edible oil comprising the diester wherein X and Y are alkenyls of 18 carbon atoms.
4. 8. A synthetic edible oil comprising the diester 6, wherein X and Y are alkenyls of 18 carbon atoms.
5. 9. A synthetic edible oil comprising the diester 7, wherein X and Y are oleyl radicals. A synthetic edible oil comprising the diester 8, wherein X and Y are oleyl radicals. of claim of claim of claim of claim of claim o r 0 00 o 0 0 00 0 00 0 0 0 000 r 00 0 W 09 I I
6. 11. A synthetic edible oil comprising a mixture of hexadecyl dioleylmalonate and dihexadecyl dioleylmalonate.
7. 12. The synthetic edible oil of claim 1 having a melting point below 10 0 C and a boiling point above 230*C.
8. 13. The synthetic edible oil of claim 1 which is absorbed by the small intestine of a mammal at a substantially lower rate than corn oil.
9. 14. The synthetic edible oil of claim 1 that provides substantially fewer calories than corn oil when consumed by a mammal. A fried food product fried in the synthetic edible oil of the claim 1.
10. 16. The food product of claim 15 with a lower metabolic fat content than a product cooked in aimal fat or vegetable oil.
11. 17. The food product of claim 15 fried in hexadecyl dioleylmalonate. 891128,csdat.066.bernard.1,9 Co C rc- 10
12. 18. The food product of claim 15 fried in dihexadecyl dioleylmalonate.
13. 19. A food product containing the synthetic edible oil of claim 1. A food product fried in the synthetic edible oil of claim 11.
14. 21. A method of frying food comprising heating the synthetic edible oil of claim 1 to frying temperature and contacting an article of food with said synthetic edible oil.
15. 22. A synthetic edible oil in accordance with claim 1 and substantially as hereinbefore described with reference to any one of the Examples. DATED THIS 28th November, 1989 DAVIES COLLISON Fellows Institute of Patent Attorneys of Australia. Patent Attorneys for the Applicant o o 0 0 00 oQ 0 o 0 S0 0 0 C 0 0 0 0 6 0 0 0 S°'C 31 32 33 34 36 37 TITI 3- 8 r iiLd/ y 89 11 28 dat.066bernard.1,1O