RU2008771C1 - Low-calorie food product - Google Patents

Abstract

FIELD: food industry. SUBSTANCE: proposed product is saturated by epoxide polyol ester having formula P/OH/_a+c/EPO/_n R(COOH)_b where P(OH) is polyol having a (number of primary hydroxyls) equal 2-8, c (number of secondary and tertiary hydroxyls) equal 0-8, a+c= 3-8, EPO - C₃-C₆ is epoxygroup, n is minimal index of epoxidation, its average value being n= a. Value of n is so that more than 95 of primary hydroxyls of polyol are inverted into secondary or tertiary hydroxyls, RCOOH is acyl fragment of fatty acid of C₇-C₂₃ acyl series where 2<b=a+c. Desired product is prepared by interaction of polyol having formula P/OH/_a+c with C₃-C₅ epoxides. The process takes place in the presence of basic catalyst within time sufficient for producing mixture of polyols elongated by polyoxide and having minimal index of epoxidation, its average value is not less than a. Thus prepared mixture of elongated polyols interacts with at least one fatty acid RCOOH to prepared mixture of polyol esters elongated by epoxide. Additionally desired product contains unfat components, their quantities are up to 90 mass% . Above mentioned R is chosen of C₁₄-C₁₈ alkyl series or of their mixture, epoxide is chosen of propylene oxide, pentene oxide, 1,2-epoxybutan, 2,3-epoxybutan, 1,2-epoxy-2-methylpropane, 1,2-epoxicyclohexane, or of their mixtures; polyol is chosen of sugars, glycerides, saccharides or their mixture (sugar being chosen of glucose, mannose, galactose, arabinose, xylose, sorbitose, amilose and their mixture); POH is glycerin; a= 2, c= 1; EPO is propylene oxide, butylene oxide or isobutylene oxide; n= 2-8, a= 2-3. Proposed polyol ester provides rate of lipase hydrolysis less than 10% of that while using olive oil. EFFECT: improves desired product quality. 12 cl, 3 tbl

Description

 The invention relates to low-calorie food compositions containing esterified epoxide-filled polyols (ENEN) as unassimilated non-nutritive fat substitutes (fatty foods) for cooking and as part of food products.

ENENs have good organoleptic characteristics and an acceptable ability to withstand general digestibility, as was established by studying by feeding rats. More specifically, the invention relates to mixtures of acylated epoxidized glycerol (AEG) compounds of the formula [P (OH) _{a + with} EPO ( _n ) FE) _b ], where a P-polyol containing primary hydroxyls a = 2-8 and secondary + tertiary hydroxyls c = 0-8, the sum of a + c being in the range of 3-8, EPO epoxide C ₃ -C ₆ , FE-acyl fatty acid residue, n is the minimum average number of epoxylation index, the value of which is generally equal to or greater than, or is a number sufficient to exceed 95% of the primary hydroxyls that are converted to secondary or tertiary s hydroxyls, and b is in the range of 2 <b <a + c, which are capable of withstanding to hydrolysis by pancreatic lipase. Received ENEP may have physical properties that are in the range of properties of liquid oil, direct fats and ordinary fats. They can be used in food and for cooking, as they have good taste and their characteristics are similar to the properties of vegetable oils and fats. Being relatively non-absorbable, non-digestible and non-toxic, they can be used as substitutes for natural or processed oils and fats, do not have a low calorie content.

 The accumulation of medical experience over the past few years regarding involvement in poor health when consuming large amounts of fats, mainly heart disorders, atherosclerosis and obesity, has caused extreme concern among consumers regarding their diet. It is estimated that 70-80% of US adult women follow diets that provide weight loss at least once a year.

 General obesity is one of the most common metabolic problems among people today. A balanced diet requires fats and oils. However, the average consumer for his own food simply consumes more of these food components than he needs. Fat in the amount of 9 cal / g compared to 4 cal / g of carbohydrates or proteins is the most concentrated dietary energy form. It is estimated that in a typical diet of Western countries, fat components provide approximately 40% of the total calories. Fats are consumed directly in meat, pasty products, salad oils and in natural products, in particular in environments and avocados. Fats and oils are consumed as a result of absorption or introduction into food during baking and frying in fat. A wide increase in the consumption of fast-cooked foods is the main reason for the increase in dietary fat, since the production of fast-cooked foods is primarily based on frying processes using fats and oils. In addition, snacks manufacturers use large quantities of fats and oils in the preparation of potato chips and other snacks. For example, according to the USDA, in 1981, approximately 12 billion pounds / 5.4431 million tons of fat and oil was used for cooking foods, mainly for baking, frying in fats, margarine, salad oil and / or when cooking in oil.

 Thus, there is currently an extremely great demand in the food market for healthy fat substitutes or fatty foods that are either completely non-digestible or low in calories. Many nutritionists believe that Americans are usually based on fats when cooking, so their calories are too high in calories. The National Research Council, for example, recommended that Americans reduce their calorie intake from fats from 40% to at least 30%. Replacing dietary fat with non-nutritive substitutes is a more effective way to reduce the amount of calories consumed than replacing sugar or carbohydrates, since replacing one gram per gram of non-nutritive substitute fat is more than twice as effective as reducing the amount of carbohydrates by replacing them with foods such as sugars or Nutra-sweet.

 One of the difficulties that you have to face when removing fat from the diet is the fact that fats and oils are widespread in foods. This is partly due to the fact that they also play an important role in the organoleptic acceptability of food products. As for fat substitutes: they must be non-digestible, i.e., not hydrolyzed in the digestive tract. In addition, they should not be directly absorbed through the intestinal wall. The threshold molecular weight of non-absorbability of the lipophilic molecules is apparently about 600.

 In addition, the fat substitute itself should be non-toxic when consumed in large quantities. It should not contain any toxic residues or impurities. To the extent that the fat substitute can be partially hydrolyzed in the digestive tract, it should not form any toxic and / or metabolized hydrolysis products. In the case of their transformation in the process of metabolism, they must have a very low calorie content. Usually, fat substitutes should not have any medical side effects.

 Fat substitutes should also have good organoleptic qualities, in particular taste, without giving any taste. Moreover, fat substitutes must have acceptable physical properties for their use in food products, i.e., they must be liquid or solid depending on their use as oil or shorning, and in the case when they are used for hot cooking They must be heat resistant. Despite the use of some polysaccharide gums as thickening additives, bulk or conventional fillers in low-calorie foods, they are able to give these products the “stickiness” felt in the mouth, not acceptable for hot cooking due to their thermal instability.

 Acceptable synthetic fats should be added in large quantities (30-60%) to salad oils, hot cooking oils, margarines, oil mixtures, mayonnaises, shornenings and the like, which allows the creation of low-calorie products of a new class. Despite the current availability of “low-calorie” mayonnaise and salad dressings, a decrease in their caloric content is achieved by increasing the water content in them, which causes a corresponding loss in the organoleptically “rich” taste of such products.

 A modern overview of this technical field is given in the article Getting The Fat Out-Researehers Seek Substitutes For Full-Fat Fat "JAOCS, Vol. 63, No. 3 / March, 1986, pp. 278-286, 288.

 One of the previously proposed fat substitutes is sucrose ester (SES), described in US Patents 3,600,186 (in the name of Matson et al., 1971), 3,521,827 and 3,936,699 in the name of Rizzi et al. 1976), owned by " procter and gamble. " Such SEA are produced by the reaction of a monosaccharide, disaccharide or sugar alcohol containing at least four hydroxyl groups with fatty acids containing 8-32 carbon atoms. In the journal Chemical and Engeneering News (07.26.1982, p. 22), it was reported that the introduction of SES as a partial replacement for fats in the diet of ten full patients reduced the amount of calories they consumed, while satisfying their need for fats. An additional positive effect was a decrease in the cholesterol content in their blood serum, a decrease in the density of lipoprotein and triglycerides, each of which causes diseases associated with fragility of arterial vessels. However, a serious drawback of SES is that they cause diarrhea and reduce the plasma of vitamin A and vitamin B.

The method for producing SES is based on methanolysis followed by esterification and extraction. The implementation of the method of producing SES involves the cost of a large amount of time for the reaction, with the addition of fresh portions of the transesterification catalyst and the excess of soybean fatty acid methyl ester (RCO ₂ Me). Of considerable importance is control of the temperature, because sucrose will char at its melting temperature ^(about 185 C). In addition, to solubilize sucrose in the esterification solution, it should be added carefully, in the form of microscopic portions of powder (obtained by grinding sucrose crystals in a hammer mill) into an RCO ₂ Me solution containing half of the amount of sucrose of an alkali metal soap. After partial esterification of sucrose added excess RCO ₂ Me and the mixture was kept at 145 ^{° C} for 8-12 hours. Used as a starting material fatty ester RCO ₂ Me is prepared by not continuous, and batch process, wherein it should be washed with water to complete glycerol removal. Technical cane sugar must be crushed to a consistency of finely divided talc-like powder with a particle size of 50 microns or less, which allows its dissolution in the reaction solution to be accelerated. In order to avoid disproportionation to sucrose, which is carbonized, and higher sucrose esters, a two-stage addition of RCO ₂ Me is necessary. For every pound of SES obtained, it is necessary to clean and recycle one pound of RCO ₂ Me. Due to the use of a large excess RCO ₂ Me selection SES is a complex process associated with the necessity of liquid-liquid extraction at a temperature of 0 ° ^C with methanol or ethanol to remove unreacted RCO ₂ Me. To obtain a product with a light color, final extraction with hexane and clay bleaching are necessary. During the cleaning process, most of the resulting product is lost.

 In the description of patent 3521827, a method for producing SES by solventless transesterification using phenyl ethers is proposed. However, phenol is released during this reaction. Since phenol is extremely toxic and corrosive, it contaminates the product, and its separation from it is fraught with technological difficulties. Thus, this method does not meet the requirements "for the synthesis of SES in the food industry. The patent specification 3963699 proposes a solvent-free transesterification comprising heating a mixture of a polyol with four hydroxyl groups, with a lower alkyl ester of a fatty acid and an alkali metal in the presence of a basic catalyst, as a result, a uniform melt is formed, and the subsequent addition to the reaction product of such a heated mixture of an excess of lower fatty acid alkyl esters, which allows get SES.

 In the description of US patent 4034093, also issued by Procter & Gamble, it is proposed to fortify SES with fat-soluble vitamins to obtain pharmaceutical compositions for treating or preventing hypercholesterolemia in living animals and for use in low-calorie foods. This mixture is valuable because eating SES causes, as indicated above, vitamin deficiency.

In the description of US patent 3818089 it is said that C ₁₂ -C ₁₈ ether glycerol analogues, glycerol alkyl esters are not digested.

 As shown by C. W. Werlm et al. In the journal Food Cosmetic Toxicol. 9 (1971) p. 479, eating monopropylene glycol (PGM) does not cause harmful effects. It is metabolized along the same metabolic pathway as carbohydrates. PGMs are currently used as a humectant in finely chopped coconut and most coconut blends. Food additives based on ethylene oxide and propylene oxide, in particular propylene glycol monostearate, are recognized food additives, the maximum allowable amounts of which are determined by law. Booth A. and Gros A. in an article entitled Calorie Availability and Digestibility of New-Type Fats, which is published in Journal of the american oil Chemists Society, vol. 40, 1963. p. 551-553, write that in studies on the feeding of rats with amylose palmitate, amylose stearate and amylose oleate, these substances were absorbed only by 17-29%. In an earlier article on the same subject by Gros A and Fudge R entitled Properties of the Fatty and Esters of Amylose, which was published in the Journal of the American oil Chemists Society, vol. 39, 1962, p. 19-24, it is said that such esters do not have distinct melting points and remain extremely viscous upon melting. Of the density, it slightly exceeds the density of the corresponding free fatty acids and glycerides. Despite the interest they presented for use in dipping coatings on both food and non-food products. The article does not contain any information regarding the similarity and functional properties of triglyceride fats in foods.

 In the book Ether Lipids, published in 1983 by Academic Press, Mangold and Paltauf provided an extensive overview of ether lipids. Trialkyl glycols having long alkyl chains are not hydrolyzed or absorbed when they feed rats. Such long-chain trialkylated glycols are non-toxic and do not affect the absorption of fats and fat-soluble vitamins. However, they are much easier to oxidize than normal fats containing comparable acyl chains, which leads to the problem of their resistance. Moreover, obtaining such compounds is a complex and expensive process.

 The description of Canadian patent 1106681, issued to Swift & Company in 1981, refers to dialkyl esters of glycerol, which, when fed to rats, are digested only in small quantities. Such mixtures exhibit the physical and organoleptic properties of ordinary fats.

 U.S. Patent 2,962,419 discloses non-pentyl alcohol esters, in particular cancer pentaerythritol cancer. These alcohols contain 1-8 hydroxyl groups and include at least one neopentyl core, while fatty acids contain at least 4 carbon atoms. It is shown that they are not hydrolyzed by pancreatic lipase. The serum of rats fed such esters contained a reduced amount of lipids. However, when studying the need for food when feeding these compounds, it was found that rats that received such esters of neopentyl alcohols ate more feed than control animals, therefore, in these two groups of animals there was no difference in weight. Thus, these compounds were not likely to satisfy, but stimulated the need for fats.

 Retrogrades are esters of fatty alcohols and tricarboxylic acids. It is reported that they are not hydrolyzed by pancreatic lipase, as a result of which they can be of value as non-absorbable fat substitutes. However, it is also reported that with the use of non-absorbable retrogers, an increase in fecal mass occurs, which is a disadvantage.

 It was proposed to use alkyl esters, in particular, 2,3-ditetradecyloxypropionic acid dodecyl ester, as a fat substitute, however, it was established in vivo in rats that they are involved in metabolism and are absorbed. At first, the cleavage of the complex alkyl ether groups occurs, and then the simple alkyl ether groups.

 According to JACS journals Volume 8 (1958) p. 6338ff and JAOCS Volume 36 (1959), p. 667ff The USDA has synthesized a series of short chain diglyceride esters of dibasic acids for potential use in food. It has been established that dicarboxylic acid distearing glyceride esters are poorly absorbed and used by rats. The distearinadipate was almost not absorbed, while adipostearin was absorbed only by 58% in experiments with rats. In contrast, oleostearic and doleic esters of dicarboxylic acids proved to be more digestible and used. The viscosity of symmetric diglyceride esters of fumaric, succinic and adipic acids exceeds the viscosity of cottonseed oil and coconut oil. They can be used as fats for baking, seasonings for fruits or surface coatings for food.

 In the description of US patent 3579548, issued to Procter & Gamble in 1971, triglyceride esters of alpha-branched carboxylic acids are proposed to be used as low-calorie fats. The absorption coefficient of these esters is in the range of about 0-50, in contrast to that of conventional triglycerides (90-100%). It has been suggested that the alpha-branched carboxylate structure prevents the hydrolysis of such compounds by pancreatic enzymes. They are proposed to be used as fat substitutes in salad oil, mayonnaise, margarine and dairy products.

 Polyoxyethylene stearate is an emulsifying agent with fat-like properties, which when consumed in food exhibits a calorie content of only 4.2 kcal / g. Its molecule is hydrolyzed to stearic acid, which is able to be metabolized, and to polyoxyethylene diol, which is excreted unchanged with excrement. In the technical literature, fat-like emulsifying agents are proposed to be used as low-calorie fat substitutes.

In the description of US patent 3337595, issued to Nalko Chemical in 1967, a method for producing fatty acid esters of polyoxypropylated glycerol of the formula glycerol (propylene oxide) _n (fatty acids) _m , the molecular weight of which is determined by the following values: n = 9-16; am = 1 or 2. It is indicated that such esters can be used to control, suppress and / or prevent the foaming of water systems that tend to foam in industrial processes. Typical examples of such aqueous systems are cellulosic suspensions used in the manufacture of paper, wastewater discharge systems, systems containing surfactants, systems containing saponias, systems containing protein, and the like. 1,2-propylene oxide is attached to glycerol to obtain polyoxypropylated glycerol (POG) with a molecular weight in the range of 600-1000. Fatty acid esters are obtained by stoichiometric esterification of POG with saturated or unsaturated aliphatic monocarboxylic acids containing chains of 12-22 carbon atoms in length. The esterification process is carried out in the range of 200-240 ^about C in vacuum, with a residual pressure of 30-50 mm RT. Art. Specific examples are stearic acid diesters of polyoxypropylated glycerol of molecular weight 700. An emulsifier is required in anti-foaming compositions, with specific examples being polyoxyethylene glycol dioleates 400. The monocarboxylic acids used to produce the diesters are acids containing 12-22 carbon atoms. There is no specific description of the triether or complete esterification with propylene oxide. There is also no description of the use of diester compounds as fat substitutes in food products.

 Gibson, W.H. and Quick, K., in an article entitled Averange Molecular Structure of Base-Catalyzed Low-Mole Adducts of Propylane Oxyde to Glycerin, which was published in J. Applied Polymer Sci. t. 14 (1970) p. 1059-1067, at a molar ratio of glycerol (G) to propylene oxide (PO) of 1: 3, all three hydroxyl groups of 63% of the addition product are propoxylated, at a ratio of 1: 4, 92% are propoxylated, and at a ratio of 1: 5, all of the starting hydroxyls are propoxylated.

 It is obvious that in the art there is a serious need for the creation of improved fat substitutes that are easy to synthesize and which are free from the disadvantages of the previously proposed compounds.

 One of the objectives of the present invention is the creation of improved non-digestible fat substitutes, which include esterified, epoxide-extended polyols (EPECs), suitable for use individually as oils for hot cooking, fats or waxes or as part of food compositions, as partial or full substitutes for fats or oils.

 Another object of the invention is to provide an non-digestible, non-absorbable, non-caloric fat substitute or similar fat that can be used in food compositions or for preparing food products.

 The aim of the invention is the creation of improved practically non-digestible fat substitutes or partial fat substitutes, which are epoxide-elongated polyols, in which the epoxylation rate is sufficient to prevent a substantial degree of pancreatic lipase hydrolysis.

The aim of the invention is also the creation of improved, practically non-digestible fat substitutes or partial fat substitutes, which are esterified with epoxy elongated polyols of the formula P (OH) _{a + c} (EPO) _n (FE) _b , where the e-xylation index n exceeds about 2, more preferably within 2-3.

 Another objective of the invention is the creation of improved fat substitutes, which are peracilated epoxide-extended polyols containing 3-8 hydroxyl groups.

Another objective of the invention is the creation of improved fat substitutes, including acylated, epoxide-extended glycerins, in which the epoxides are C ₃ -C ₆ epoxides.

 The aim of the invention is the creation of improved fat substitutes, including acylated, elongated propylene oxide glycerols, the propoxylation rate of which n exceeds about 2, preferably in the range of 2-3.

Another objective of the invention is the creation of improved fat substitutes, including esterified, epoxide-extended polyols, more preferably acylated, propylene oxide-extended glycerins, in which the acyl esters are C ₈ -C ₂₄ compounds and in which pancreatic lipase hydrolysis is compared to olive oil, determined in vitro is less than about 10.

 An additional objective of the invention is the creation of acylated, elongated with epoxide polyols, in which the size of the acyl groups is sufficient to prevent their absorption through the walls of the digestive system, the epoxylation rate is large enough to substantially prevent hydrolysis, and which have good organoleptic properties, their products and their hydrolysis are non-toxic.

The aim of the invention is also the creation of improved fat substitutes, which are triacylated polypropoxylated glycerols, in which the propoxylation index exceeds about 2, preferably about 5 or more, and the acyl groups are residues of compounds C ₈ -C ₂₄ , more preferably C ₁₄ -C ₁₈ , and in which the lipase hydrolysis rate is less than about 10.

 Another objective of the invention is the creation of food compositions and products that use the fat substitutes of the present invention.

 In accordance with the present invention, there are provided esterified, filled with epoxides polyols (ENEPS), and use as non-digestible fat substitutes (fatty similarities), characterized by low-calorie nutritional value, which have good organoleptic characteristics, substantial absorption resistance when consumed and without noticeable hydrolysis in the digestive tract.

The structure of the non-digestible fat substitutes of the present invention can be generally characterized by the formula P (OH) _{a + c} (EPO) _n - (RCOOH) _b , where P / OH is a polyol containing a = 1-8, primary hydroxyls and c = 0- 8 secondary + tertiary hydroxyls, the sum of a + c being in the range of 3-8, EPO epoxide C ₃ -C ₆ , r is the minimum average value of the epoxylation index, the value of which is usually equal to or greater than "a", this value should be sufficient so that over 95% of the primary polyol hydroxyls are converted to secondary or tertiary idroksily, RCOOH-fatty acid residue wherein R - alkyl chain with 7 or more carbon atoms, and preferably when RCOOH contains 8-24 carbon atoms and in average number in the range 2 b (a + c).

The class of acceptable polyols encompasses sugars, glycerides or saccharides that react (esterify) with C ₃ -C ₆ epoxides, in particular with propylene oxide, butylene oxide, isobutylene oxide, pentenoxide and the like, with the formation of epoxide-filled polyols (CNPs), a minimum value epoxylation of which is 2, and is usually in the range of 2-8. Sugars can be selected from glucose, mannose, galactose, arabinose, xylose, sorbitol, amylose and the like.

/_x
(где значения сумы d+e+f= n, который определен выше, сумма х+у+z= b, который определен выше, R¹= R²= Н, R³= Н или алкил, R⁴-алкил, а R⁵-C₇-C₂₃, предпочтительное С₁₃-С₁₇. В том случае, когда в качестве эпоксида используют пропиленоксид, каждый из R¹-R³-водородный атом, R⁴-Me(метил), сумма d+e+f, показатель эпоксилирования (пропоксилирования), равен 2-8, предпочтительнее примерно 3-5, если основываться на пределенном на витро действии липазы поджелудочной железы при сопоставлении с оливковым маслом.Prefer triolglycerol, the final formula of which is given below:

/ _x
(where the values of the sum are d + e + f = n, which is defined above, the sum x + y + z = b, which is defined above, R ¹ = R ² = Н, R ³ = Н or alkyl, R ^{4 is} alkyl, and R ⁵ -C ₇ -C ₂₃ , preferably C ₁₃ -C _17. In the case where propylene oxide is used as an epoxide, each of R ¹ -R ^{3 is a} hydrogen atom, R ⁴ -Me (methyl), the sum is d + e + f, the rate of epoxylation (propoxylation) is 2-8, preferably about 3-5, if based on the limit on the vitro action of pancreatic lipase when compared with olive oil.

The epoxylation rate is high enough so that the final ENECs are resistant to absorption in the digestive tract and in vivo digestion due to nonspecific assimilation by lingual lipases. In this regard, two factors must be considered. The first of these is the epoxylation index for non-digestibility, and the second is the length of the acyl chain for nonabsorption. In the case when the threshold of indigestibility in vivo is, as established, n = 4, then the limit of the length of the acyl chain R ⁵ for direct absorption could be only C ⁷ (octanoate ester). The average molecular weight of such varieties of molecules (using glycerol and propylene oxide) could be 702, but since the mixture contains distributed compounds by molecular weight, it can include compounds with mol. M. 586 and 644.

Esters of tertiary alcohols (R ³ = alkyl R ⁴ ) or secondary alcohols with bulky substituents are able to provide good protection against lipase hydrolysis. So, for example, you can use 1,2-epoxybutane (R ⁴ -ethyl), 2,3-epoxybutane (R ² = R ⁴ -methyl), both butylene oxide, 1,2-epoxy-3-methylpropane (R ³ = R ^4- methyl), isobutylene oxide, 1,2-epoxycyclohexane and the like.

It must be borne in mind that the epoxidation index covers mixtures obtained by the reaction of a polyol with an epoxide catalyzed by a base. Thus, when glycerol and propylene oxide are used in combination with C ₁₆ -C ₁₈ fatty acids, it was found that, in comparison with olive oil, which is a typical substrate with a degree of reactivity with in vitro lipase of 100, the degree of hydrolysis with a propoxylation index of 2 or more, it is about 20-30% of the degree of hydrolysis of olive oil. Indigestibility is understood to mean a degree equal to less than about 20%, more preferably 10%. Thus, good food products could be made or prepared by hot processing using a mixture of natural fats with synthetic similar fats of the present invention, which combine in ratios that provide any given caloric content of fats. In the case where n is 4-5, the relative degree of exposure to lipase is zero. Depending on the desired organoleptic properties, the amount of the introduced substitute can vary from a few percent to partially reduce calorie content to a complete replacement in the preparation of non-nutritive foods. Conversely, in the case where the obtained EHEC has a relative lipase effect close to 20, various amounts of the EHEC fat substitute of the present invention can be added to the mixture to achieve the desired organoleptic properties or to provide a specific usefulness for hot cooking (for example, the ratio between oils and fats).

H₂-O-CH₂-CHCH₃-O-COR
И наоборот, в том случае, когда n= а, например n= з или более для глицерина, соединения настоящего изобретения ЭНЭП включают в себя полиэпоксиды в удлиненной эпоксидами внутренней связи между полиолом и остатками ациловых эфиров. Так, например, для пропиленоксида присутствуют связи -(-СНСН₃-СН₂-0-)_f- и /или -(-СН₂-СНСН₃-0-)_f где f-2 или более. Эти последние связи доминируют. Неусваиваемость ЭНЭП настоящего изобретения обусловлена тем, что спиртоэфирная связь является скорее вторичной, чем первичной.So, for example, in the case of glycerol and propylene oxide, where a = 2, c = 1, n = 2, and b = 3, the resulting main compound is triacyl -1,3-di- (2-hydroxypropyl) -glycerol

H ₂ -O-CH ₂ -CHCH ₃ -O-COR
Conversely, in the case where n = a, for example n = z or more for glycerol, the compounds of the present invention ENEP include polyepoxides in the epoxy-extended internal bond between the polyol and the residues of acyl ethers. For example, for propylene oxide there are bonds - (- CHCH ₃ —CH ₂ —0—) _f - and / or - (—CH ₂ —CHCH ₃ —0—) _f where f is 2 or more. These last connections dominate. The non-digestibility of the ENEP of the present invention is due to the fact that the alcohol-ether bond is more likely secondary than primary.

As a result of acylation with one or more C ₈ -C ₂₄ fatty acids, an ester is formed as a final product with physical properties from liquid oil to fatty and solid fats, and even to waxes. The final ENEP can be used in food compositions and for hot cooking, since they have good taste qualities, and their characteristics are similar to those of vegetable oils and fats. Being relatively non-absorbable, non-digestible and non-toxic, they can be used to replace natural or processed oils and fats, but do not have any value in terms of calories.

 Examples of such fatty acids are caprylic, capric, lauric, myristic, myristoleic, stearic, palmitic, palmitoleic, ricinoleic, linoleic, linolenic, eleostearic, arachinic, behenic, erucic, oleic and / or heptadecane. Such fatty acids can be obtained from the corresponding naturally occurring or synthetic fatty acids, they can be saturated or unsaturated, include positional isomers and geometric isomers depending on the desired physical properties (for example, a liquid or solid fatty product.

Fatty acids per se or naturally occurring fats and oils can serve as a source of the fatty acid component. For example, rapeseed oil is a good source of C ₂₂ fatty acid. C ₁₆ -C ₁₈ fatty acids can be derived from solid fat, soybean oil, or cottonseed oil. Shorter chain fatty acids can be derived from coconut oil, palm kernel oil, or Babasu Brazil nut oil. Corn oil, fish oil, melted pork fat, olive oil, palm oil, peanut oil, safflower oil, sesame oil, jojoba oil and sunflower oil are examples of other natural oils that can be the source of the fatty acid component. Among the fatty acids, those are preferred which contain from about 14 to 18 carbon atoms, the most preferred being selected from the class that encompasses myristic, palmitic, stearic, oleic and linoleic acids. Preferred sources of fatty acid components are natural fats and oils that are high in these fatty acids, such as soybean oil, olive oil, cottonseed oil, corn oil, hard fat, and melted pork fat.

Best embodiments of the present invention include mixtures of acylated propoxylated glycerol compounds (APGs) of the formula [G (PO) _n (FE) _b -], where G is glycerol (i.e., a = 2, and c = 1 in P ( OH) _{a + c of the} above formula, (PO-propylene oxide, FE-residue of a fatty acid ester, the average number of propoxylation and is in the range from 2 to 5, and the average number b is from more than 2 to 3. The class of acceptable fatty acids includes mixtures of palmitic acid or heptandecanoic acid with oleic acid. These APGs are resistant to hydro lysis of pig pancreas lipase, a dominant enzyme in the digestion of fat in vitro.

 Even in the case where the residues of the fatty acid are cleaved by hydrolysis from the ENEP and APG molecules of the present invention, no evidence of toxicity of the formed UEP was found in the studies. In fact, even propylene glycol, which could be released as a result of the cleavage of the ether link of the UEP, has received the status of VPB from the Food and Drug Administration for quality control (generally recognized as safe). Propylene glycol and its derivatives are used in small quantities in the food industry, for example, as solvents for flavorings and pharmaceutical substances, as well as in baked goods, seasonings for salads and sauces.

When carrying out the method of the present invention, a reaction catalyzed by a base (preferably an alkali metal) polyol with an epoxide is provided. As indicated in the aforementioned article by Gibson and Quick, the main catalysis leads to the opening of the oxirane ring of propylene oxide during the addition reaction, as a result of which mainly secondary hydroxyl groups are formed (in the ratio of about 98% secondary to 2% primary). In the case of glycerol, it is preferred to start from a fat such as soybean oil, which is broken down to produce glycerol and RCO ₂ H, and the glycerin is separated from the fatty acid. As a result, glycerol is obtained for the base-catalyzed addition reaction by propoxylation. Then reacted resultant G (PO) _n, preferably wherein n = 2-5, at a high speed at an elevated temperature in approximately 100-200 ^{° C,} in the presence of p-toluenesulfonic acid (PTSA) with a stoichiometric amount of the soybean oil fatty acid, whereby a mixed APG product is formed. The obtained APG can be cleaned and bleached by conventional methods, for example using alkali and clay, to obtain a pure product with a weak color and low acid number.

 The following detailed description is given as an example of the basic principles of the present invention, to which its scope is not limited, in order to illustrate the best embodiment of the invention.

In this example, the epoxide (EPO) is represented by propylene oxide (PO), the polyol P (OH) _{a + c} is glycerol (G), and the acyl residue of the esterified fatty acid (FE) is a mixture of either palmitic or heptadecanoic acid with oleic acid, resulting what do edible oil (fat substitute) get like a fat formula
[G (PO) _n (FE) _b ], where n = 2-5, and b = 3. When 5 units of PO are attached, all hydroxyls of the starting polyol) in this triol example) undergo simple esterification (in this example, propoxylation).

 PRI me R 1. 1. Synthesis of propoxylated glycerol. A. Obtaining a catalyst.

A solution of the catalyst for the propoxylation reaction is prepared so as to have 0.25 wt. % potassium ions per 6000 g of the final propoxylated product. To obtain a catalyst, 27.59 g of powdered potassium hydroxide and 300 g of glycerol (G) are charged into a 1000-milliliter flask of a rotary evaporator and in a stream of nitrogen (the contents of the flask are kept at a temperature of 75-80 ^о С with stirring for 1 h. The catalyst passes in solution, forming a cloudy mass which is subjected to distillation in a rotary evaporator at 60-70 ^C under a residual pressure of 5 mm Hg. v. over 1 to remove water. The theoretical water loss is 12.98 g The catalyst solution (314.62 g) add to a dry reactor with a capacity of 2 gallons (7.571 liters) stainless steel purged with a stream of nitrogen.

 B. Propoxylation reaction: G: PO ratio is 1: 3.

To obtain propoxylated glycerol with three hydroxypropylene units, the starting glycerol was charged in an amount of 2073.32 g, i.e., 1773.32 g was loaded as free glycerol and 300 g was added together with the catalyst). The remaining 1773.32 g of glycerol (mol. M. 92.1) (mol) was added to the reactor under conditions of purging with a stream of dry nitrogen. The reactor was heated to 70-75 ^{° C} and nitrogen pressure was adjusted to about 20 lb / sq. inch 1.41 kg / sq. see Initially loaded with 500 g of propylene oxide (PO) mol. m. - 58.098 g (mol) of the reactor due to the reaction exotherm and the temperature rose to 90 ^C. After the reaction temperature was brought to 90-95 ^C and the remaining dry propylene oxide was added depending on the required pressure during the 18-hour period. To control the rate of addition, a control valve system was used to maintain the desired pressure. Reference pressure was set at 60 psi. inch. 4.22 kg / sq. see. In the case when the pressure inside the reactor went down to a level lower than the set one, the control valve opened and more propylene oxide entered the reactor. In the case when the pressure increased to a level exceeding the set, that is, 60 psi. inch, 4.22 kg / sq. see, the valve was closing. Propylene oxide was contained in a container, which was suspended in a weight measuring mass dose, which allowed loading the exact amount of propylene oxide. To produce propoxylated glycerol with three hydroxypropylene units, the total amount of propylene oxide charged is 39.26.68 g. Since the nitrogen pressure in the vessel is 80 psi. inch, 5.62 kg / sq. cm total pressure in the reactor rises to 80 psi. inch, 5.62 kg / sq. cm, when all propylene oxide was transferred from the weight measuring mass dose to the reactor. After the introduction of the entire amount of propylene oxide, the reaction mixture was subjected to additional cooking for another 4-6 hours, which ensured the completeness of the reaction.

After completion of the reaction, the product was removed hot from the reactor and was treated product magnesol ^R (4 grams per 250 grams product) for 2 hours at a temperature of ^about 100-110 C. to remove catalytic potassium ions. The product obtained was subjected to suction filtration by passing the material through celite ^R (purified diatomaceous silica) bed at a temperature of 60-80 ^{° C} to give the pure oligomeric polyol. To determine the characteristics of the oxypropoxylated mixture of glycerols (OCG), we used the data for the determination of the hydroxyl number, mol. m. VPO, gel permeation chromatographic analysis (GPC) and C ^13- NMR spectral analysis. According to GPC analysis, the polydispersity for OPG with three hydroxypropylene units is 1.19, and mol. m. calculated by the hydroxyl number is 266 g / mol.

II. Synthesis of APG (triacylated OPG). During a typical synthesis, a solution of 0.335 mol of repeated distilled acyl chlorides (a mixture of either palmitoyl or heptadecanoyl chlorine with oleoyl chloride in a 1: 5 molar ratio) in 20 ml of dry chloroform is added dropwise to a stirred solution of 0.01 mol. OCG in 20 ml of dry chloroform and 6 ml of dry pyridine. The addition operation is carried out at room temperature in an atmosphere of dry nitrogen and stirring is continued for an additional 24 hours. Phase separation occurs in the reaction vessel. At the end of the reaction, the mixture is added to 500 ml of water and extraction is carried out several times in 3 portions of 500 ml of petroleum ether. The combined organic phase is then washed with 2 portions of 500 ml of water, 2 portions of 500 ml of a dilute aqueous solution of hydrochloric acid, 2 portions of 500 ml of water, 2 portions of 500 ml of an aqueous solution of potassium bicarbonate, and then 2 portions of 500 ml of water and dried over anhydrous sodium sulfate, followed by evaporation of the solvent. Prior to column chromatography, all remaining free fatty acids were methylated with ether diazomethane. Mixtures of crude acylated propoxylated glycerols (APGs) obtained as products are purified by passing through a column of silicic acid, eluting with an increase in the gradient of diethyl ether in petroleum ether from 0 to 100%. The total yield for the synthesis of APG is in the range of 59-75%. The purity and structure of the APG product is confirmed by IR and ¹ H-NMR spectroscopic analyzes, as well as thin layer chromatographic analysis (TLC).

All obtained APG products at room temperature are oils and are usually characterized by a very acceptable pale yellow color, but they can be easily bleached or lightened by passing through charcoal. APGs showed reversible viscosity, with a product with n = 1 and n = 2.2 (see Example 2 below) being slightly more viscous than olive oil, and products with n = 5 and n = 8 were slightly less viscous than olive oil butter. Similarly, products with n = 1 and n = 2.2 are not solidify at 5 ^{° C,} whereas when n = 1 and n = 2.2 as they exhibit partial crystallization at 5 ° ^C intervals of molecular weights was determined as follows : n = 1.884-1000, n = 2.2 942-1116, n = 5, 1058-1290, and n = 8, 1058-1348, suggesting trioleoyl derivatives and including 95% of the total weight of polymer mixtures. All products showed organoleptically acceptable properties, possessing a gentle, oily taste without stickiness.

 III. An in vitro APG test (n = 1-8) to determine pancreatic lipase digestibility.

 PRI me R 2. In accordance with the procedure of the above example 1, a number of ACE products of the EUEC of the present invention were obtained, in which n values were varied in the range of 1-8 by controlling the amount of PO in the reaction mixture of 100 mg of APG fat or oil of the present invention, intended for testing, add in 10 ml of buffer containing 1 mmol. sodium chloride, 1 mmol. calcium chloride, 3 mmol. deoxycholate, 2 mmol. Tris and 10 g / l Arabian gum. This mixture is shaken vigorously in a closed tube and the emulsion is transferred to a pH-static reaction vessel. The pH value is titrated to 8.0 using a pH-stat Radiometer (includes the TTA80 titration system, the TTT80 titrator, the automatic burette ABU80 and the pH meter pHM82). Pig pancreatic lipase is added (0.1 ml, equivalent to 1000 enzyme units at a pH of 8.0), the pH quickly returns to 8.0, and then the reaction is carried out over a 20-minute period by autotitration with 50 mmol of an aqueous solution of sodium hydroxide. Initially, the linear speed indicates the number of micromoles of sodium hydroxide per 1 h, which is necessary to maintain the pH at a constant level by neutralizing free fatty acids released by pancreatic lipase.

 The results are summarized in the following table. 1, where they are expressed as average values of 4 determinations when compared with olive oil, taken as a control standard (100%), where EPO-RO, and FE values are similar to those described above in example 1, part II.

 If based on the data of the above table. 1, then at n = 3 the degree of lipase hydrolysis is approximately 10%, and at n = 4 it is approximately 5%. A degree of lipase hydrolysis of less than about 10% is preferred.

 The corresponding acetate adducts of APG, the test results of which are summarized in table. 1 (n = 1, 2, 2, 5, and 8), were tested by gas-liquid chromatographic analysis (column with packing) in order to show the distribution of polypropylene oxide units in each of them. The results are shown in table. 2.

 The distribution of polyepoxide units (see table. 2).

The above components represent 90% of the mass trace integral with the exception of G (PO) ₈ , where this value was 67.8% due to the presence of unknown additional components (not triacetin). % of the area is incorrect to obtain mass or molar percent (FID reaction factors are not known).

 In the case when the average molecular weight of the APG product is too small, below about 600-900, it cannot be used as an indigestible fat substitute, since it is able to be absorbed directly in the intestine. The digestibility of the APG product of the present invention is due primarily to the presence of ether bonds of secondary alcohols.

 IV. In vivo test.

 PRI me R 3. The study by feeding.

 Weaners of male Sprague-Dowley rats were kept on a diet that included 2.5 wt. % of two different test compounds, i.e. using either compositions with n = 2.2 or compositions with n = 5 of Example 2, each of which contained 18% heptadecanoic acid as the label substance, while the rest of the fatty acid residue ( acyl) in the test compound of the EPEC is oleic acid. The total amount of lipid in the diet was maintained at 10 wt. % with the addition of 2.75 wt. % corn oil, and the laboratory ration already contained 4.5 wt. % lipid. In addition, in the diet in an amount of 0.25 wt. % was also introduced indigestible label substance. which was 1,2-didodecyl-3-gecoadecylglycerol.

 The experiment with feeding was continued for three weeks, and during this entire period of time, the weight gain of the animals occurred at the same rate as in the control animals. No external signs of toxicity were found. The experiments were collected and analyzed for lipid content using a gas-liquid chromatographic analysis method based on the use of heptadecanoic acid and 1,2-didodecyl-3-hexadecylglycerol as label substances. The data obtained demonstrate the following degree of recovery as a percentage of heptadecanoic acid (HDA) in feces.

 The percentage indicated in the column entitled% HDA as a free fatty acid is the percentage of the test compound that was not absorbed, but the remainder of the HDA was hydrolyzed in the intestine or in experiments by digestive enzymes or by the action of microorganisms. The percentage shown in the column under the heading “% esterified HDA” indicates the percentage of the compound remaining in its original form, that is, not hydrolyzed in the intestine or excrement. The last column shows the total percentage of the two previous columns, which indicates the percentage of the compound that has not been absorbed or digested.

 These data indicate that the tested compounds, in particular n = 5 compounds (pentaoxypropylglycerol), show sufficient resistance to general digestion, which includes hydrolysis and absorption in the rat anterior intestine and certain hydrolysis and consumption of microorganisms of the cecum, colon and feces.

 The above synthesis using propylene oxide can be carried out by epoxylation with butylene oxide and isobutylene oxide to obtain the corresponding epoxide-extended polyols, which are then subjected to acylation, preferably peracylation, as described above.

Claims (12)

1. A LOW-CALOR FOOD PRODUCT, characterized in that it is an epoxide-filled polyol ester of the formula: P (OH) _{a + c} (EPO) _n (RCOOH) _b , where P (OH) _{a + c} is a polyol with the number of primary hydroxyls a = 1 - 8, with the number of secondary plus tertiary hydroxyls c = 0 - 7, a + c = 3 - 8, (EPO) _n - C ₃ - C ₆ epoxy group having a minimum epoxidation index n and on average n = a, satisfies the condition under which more than 95% of the primary polyol hydroxyls are converted to primary or tertiary hydroxyls, RCOOH is a fatty acid with a C ₇ - C ₂₃ chain, and c satisfies the condition 2 <b ≅ a + c, which can be obtained by reacting a polyol of the formula P (OH) _{a + c} in the presence of a basic catalyst with C ₃ - C ₆ epoxides for a time sufficient to obtain a mixture of polyoxide elongated polyols with a minimum epoxidation index, the average value of n of which at least a, in which more than 95% of the primary hydroxyls of these polyols are converted to secondary or tertiary hydroxides, and the interaction of the specified mixture of epoxy-extended polyols with at least one RCOOH fatty acid.  2. The product according to p. 1, characterized in that it additionally contains non-greasy components in an amount of up to 90 wt. %  3. The product according to p. 1, characterized in that the polyol ether has a value of n, providing a lipase hydrolysis rate of less than 10% of the hydrolysis rate when taking olive oil.  4. The product according to p. 1, characterized in that n = 2 to 8.  5. The product according to p. 1, characterized in that R has a value that provides resistance to absorption by the digestive tract. 6. Product, wherein R is selected from C ₁₃ - C ₁₇ chains or mixtures thereof.  7. The product according to p. 1, characterized in that the epoxide is selected from the range including propylene oxide, peptene oxide, 1,2-epoxybutane, 2,3-epoxybutane, 1,2-epoxy-2-methylpropane, 1,2- epoxycyclohexane and mixtures thereof.  8. The product according to paragraphs. 1 to 6, characterized in that the polyol is selected from a series excluding sugars, glycerin, saccharides and mixtures thereof.  9. The product according to p. 7, characterized in that the sugar is selected from the range including glucose, mannose, galactose, arabinose, xylose, sorbitol, amylose and mixtures thereof. 10. The product according to paragraphs. 1 - 6, characterized in that P (OH) _{a + c} represents glycerin, a = 2, c = 1, EPO - propylene oxide, butylene oxide or isobutylene oxide, n = 2 - 8a, a> 2 - 3.  11. The product according to p. 9, characterized in that n = 2 to 5, b = 3.  12. The product according to p. 10, characterized in that n = 3 to 5.

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