MXPA01009411A - Anti-oxidant - Google Patents

Abstract

There is provided an anti-oxidant composition comprising a cyclic compound having formula (I) or a derivative thereof, wherein R1 and R2 are independently selected from -OH,=O, wherein R3 is a substituent comprising an -OH group;and wherein R4 and R5 are other than H;with the proviso that the compound is other than ascorbic acid.

Description

ANTI-OXIDANT DESCRIPTIVE MEMORY The present invention relates to an antioxidant composition. Antioxidants are required in many applications, for example, as food preservatives. The degradation of food from several sources has been recognized in the literature and individual chemicals are known that will inhibit one aspect or another of the degradation derived from a single source. It is known that the degradation, loss of color or taste of parts of recently cut plants is caused by oxidation, enzymes, microbes, and metal ions. For example, acidulants are known to prevent microbial degradation by maintaining an environment with a relatively low pH, but their effectiveness has only been temporary. Fatty bodies have a tendency to oxidize, even at room temperature and this oxidation (or rancidity) makes them acquire new properties, mainly taste or smell, which are considered undesirable when these fatty substances are incorporated, for example, into compositions food or in cosmetic compositions.

These are commonly used, in compositions containing bodies or fatty materials, protective agents which, in fact, play the role of an anti-oxidant. Among the known anti-oxidants, ascorbic acid is usually used which acts mainly by direct absorption of oxygen. However, ascorbic acid is only slightly soluble in fatty acids and consequently is difficult to use in order to protect the fatty material against oxidation. Furthermore, although ascorbic acid can inhibit enzymatic darkening, it promotes nonenzymatic darkening. Therefore, it can not be used in several applications. In order to solubilize the ascorbic acid molecule in fatty materials, it has been proposed to use several ascorbyl esters such as, for example, ascorbyl stearate, palmitate or laurate; see, for example, the article by C. F. Bourgeois, "Revue Francaise des Corps Gras", No. 9, pages 353-356 (September 1981). It is also known that, in addition to their antioxidant properties, these ascorbic acid derivatives have the property of improving the activity of anti-oxidant agents such as tocopherols or caffeic acid and their esters, by promoting the regeneration of these antioxidant agents; see for example H. S. Olcott, "Oil Soap", 18, (1941), 77 and E.U.A. A-2,462,663.

Several improvements of these binary anti-oxidant agents, ascorbic derivatives + tocopherols or ascorbic derivatives + types of caffeic derivatives have been proposed, by providing the addition of a third constituent which again improves the anti-oxidant effects. Among the third constituents of these ternary systems, we can mention, mainly, p-aminobenzoic acid (EUA-A-2,462,633), phospholipids (RW Riemenschneider et al., "Oil Soap" 1941, 47) and amines (Klaui, "The Functional (Technical) Uses of Vitamins ", ed by M. Stein, University of Nottingham Seminar Vitamins, London, England, 1971, page 110). It is also known that sulfating agents that include sulfur dioxide, sodium sulfite, sodium and potassium bisulfite and sodium and potassium metabisulfite act as anti-oxidants and possess the ability to preserve plant food products. Sulfites have also been used as preservatives in prepared foods such as flavored drinks, syrup, wine and vinegar concentrates as well as in the processing of sugar, corn starch and shrimp. Due to the recent increase in reported allergic reactions to these compounds, their use has fallen into disapproval. Regulatory actions involving the use of sulphites have been initiated and the formal status of the use "generally recognized as safe" GRAS of sulphites in raw foods and vegetables has been banned by the Food and Drug Administration of the US Government. (U.S. Government Food and Drug Administration). Additional marking requirements have been imposed by the Food and Drug Administration on packaged foods that contain direct or indirect sulphite additions. Synthetic anti-oxidants are known for food products, such as dibutylhydroxytoluene (BHT) and butylhydroxyanisole (BHA). These compounds are, however, disadvantageous in that their amounts to be added to the food products must be strictly controlled. For example, a maximum allowable content of BHT or BHA in fats and oils or in butter under Japanese safety regulations should not exceed 0.02%, such limitations leading to approximately an insufficient anti-oxidant effect in some cases. In addition to the aforementioned anti-oxidants for foodstuffs, several compounds have been proposed, for example the alpha / omega-bis (2,5-dihydroxyphenyl) alkanes are described in Japanese Patent Publication No. 48-39930. The compounds, however, have drawbacks in their synthesis and effectiveness. Generally, anti-oxidants that originate from natural products are preferred to synthetic anti-oxidants as food additives from the viewpoint of safety and taste. Document EUA-A-4195101 proposes the use of a 2 ', 6'-dihydroxy-9- (2,5-dihydroxy-phenyl) octylphenone anti-oxidant. It is thought that this compound serves as an anti-oxidant in food products, such as shortening or the like, exhibiting greater anti-oxidant activities than the conventional anti-oxidant BHA. Document EUA-A-41955101 describes the preparation of the compound by extraction and separation of macia, or Hautt aromatic nutmeg (a known species) successively with petroleum ether, diethyl ether, n-hexane and carbon tetrachloride, followed by chromatographic separation. in column. According to a first aspect of the present invention there is provided an anti-oxidant composition comprising a compound having the Formula I Formula I or a derivative thereof, wherein R and R2 are independently selected from -OH, = O, where R3 is a substituent comprising a -OH group; and where R4 and R5 are different from H; with the proviso that the compound is different from ascorbic acid. According to a second aspect of the present invention, there is provided a method for the prevention and / or reduction of oxidation of a material, the method comprising the step of contacting the material with a cyclic compound having the Formula I Formula I or a derivative thereof, wherein R1 and R2 are independently selected from -OH, = 0, where R3 is a substituent comprising a -OH group; and where R4 and R5 are different from H; with the proviso that the compound is different from ascorbic acid. According to a third aspect of the present invention, there is provided a method for the prevention and / or reduction of oxidation of a material, the method comprising the step of contacting the material with a cyclic compound having the Formula I Formula I or a derivative thereof, wherein R1 and R2 are independently selected from -OH, = 0, where R3 is a substituent comprising a -OH group; and where R4 and R5 are different from H; with the proviso that the compound is different from ascorbic acid. Preferably the material is a plant or fungal material. The present invention can provide an anti-oxidant which upon contact with a plant or fungal material reduces and / or prevents discoloration of the plant or fungal material. Therefore, in additional aspects, an anti-browning composition and a method and the use thereof are provided.

According to a fourth aspect of the present invention, there is provided an anti-browning composition comprising a cyclic compound having the Formula I Formula I or a derivative thereof, wherein R1 and R2 are independently selected from -OH, = 0, where R3 is a substituent comprising a -OH group; and where R4 and R5 are different from H; with the proviso that the compound is different from ascorbic acid. According to a fifth aspect of the present invention, there is provided a method for the prevention and / or reduction of obscuration of a plant or fungal material with a cyclic compound having the Formula I Formula I or a derivative thereof, wherein R1 and R2 are independently selected from -OH, = O, where R3 is a substituent comprising a -OH group; and where R4 and R5 are different from H; with the proviso that the compound is different from ascorbic acid.

According to a sixth aspect of the present invention, there is provided the use of a compound for the prevention and / or reduction of darkening of a plant or fungal material with a cyclic compound having the Formula I Formula I or a derivative thereof, wherein R1 and R2 are independently selected from -OH, = O, where R3 is a substituent comprising a -OH group; and where R4 and R5 are different from H; with the proviso that the compound is different from ascorbic acid. In the present specification, by the term "anti-browning composition" is meant a composition which in contact with plant or fungal material, in particular fruit or vegetable material, reduces and / or prevents discoloration of the material when compared to the material when they do not get in touch with the composition. Without being limited by theory, it is believed that the anti-browning agent of the present invention reduces and / or prevents discoloration caused by the chemical and enzymatic process, for example by the inhibition of polyphenol oxidase. Preferably, the compound of the present invention is of the general formula II Formula II or a derivative thereof; where R1, R2, R3, R4, and R5 are as defined above. Preferably, the compound of the present invention is of the general formula III Formula III or a derivative thereof; where R1, R2, R3, R4, and R5 are as defined above. Preferably, the group R3 of the general formula is or comprises a group - (CH2) n-OH, where n is from 1 to 20, on is from 1 to 10, on is from 1 to 5, on = 1, 2, or 3. Preferably, the group R3 of the general formula is or comprises a group -CH2OH. Preferably, the groups R4 and R5 of the general formula are independently selected from -OH, = O or represents a bond with an adjacent atom in the ring of the cyclic compound.

The groups R4 and R5 of the general formula can independently be a hydrocarbyl group. The term "hydrocarbyl group" as used herein means a group comprising at least one C and H and may optionally comprise one or more other suitable substituents. Examples of said substituents may include halo-, alkoxy-, nitro-, hydroxy, carboxyl, epoxy, acrylic, hydrocarbon, N-acyl, or cyclic groups, etc. In addition to the possibility that the substituents are a cyclic group, a combination of substituents can form a cyclic group. If the hydroxycarbyl group comprises more than one C then those carbons do not necessarily need to be linked together. For example, at least two of the carbons may be linked by a suitable element or group. Therefore, the hydrocarbyl group may contain heteroatoms. Suitable heteroatoms will be apparent to those skilled in the art and include, for example, sulfur, nitrogen and oxygen. The groups R4 and R5 of the general formula can be independently selected from alkyl, alkenyl, cycloalkyl and aryl or can together represent an alkylene. Preferably, the cyclic compound of the general formula comprises a five or six membered ring. Preferably, the compound of the general formula is selected from ascopyrones, kojic acid, and mixtures thereof. Preferably, the compound of the general formula is a compound selected from Ascopirone M, Ascopirone P, Ascopirone T, Ascopirone Ti, Ascopirone T2, kojic acid, and mixtures thereof. Therefore, according to a third aspect of the present invention there is provided an anti-oxidant comprising a compound selected from Ascopirone M, Ascopirone P, Ascopirone T, Ascopirone Ti, Ascopirone T2, kojic acid, and mixtures thereof. same. The compounds of the present invention can provide strong anti-oxidant activity. For example, the compounds can prevent and / or delay the oxidation of carotenes and can prevent and / or delay the oxidative degradation of polyunsaturated fatty acids. In particular, ascopyrones and kojic acid of the present invention provide strong anti-oxidant activity. The use of ascopyrones in the present invention has been found particularly advantageous for at least two reasons. Ascorbic acid is a standard anti-oxidant which is considered "safe for food". Ascopyrones have been found by applicants to be 100 times more potent as anti-oxidants than ascorbic acid. In other words, to achieve the same effect as a given amount of ascorbic acid, as little as one hundredth of the amount of ascopirone may be required. Second, the production cost of ascopyrones may be approximately one tenth of the cost of ascorbic acid. Ascopirone is a known compound. In 1978 and 1981, a group of North American scientists prepared ascopirone P by pyrolysis at the Wood Chemistry Laboratory in Montana, with the intention of using ascopirone P as an initial material for organic synthesis [1-2]. They characterized ascopirone P by, for example, H and 13 C NMR techniques, and IR spectroscopy. A 3-dimensional structure of ascopirone P was obtained. The yield of ascopirone P obtained by pyrolysis was only 1.4% and complicated separation methods had to be used. The natural occurrence of ascopirone P in some very sparsely studied fungi species collected from the Alps has been taught [3]. The occurrence of ascopirone P in fungi immediately instigated the hypothesis that ascopirone P could act as an antibiotic. Nevertheless, ascopirone P does not work satisfactorily as an antibiotic in the tests described. The preparation of ascopirone P from anhydrofructose by a chemical method was described in [4]. The six molecules of ascopirone are known, the formula of which is shown in the following structures. However, its use as anti-oxidants is new.

Ascopirone M Ascopirona P Ascopirone T Ascopirona T., Ascopirona T2 Ascopirona T3 Ascopirone P and ascopirone T can be produced from 1,5-anhydro-D-fructose by EDTA-sensitive dehydratases isolated from fungi of the order Pezizales, such as Plicaria leiocarpa and Anthracobia melaloma, and of the order of Tuberales, such as, Tuber melanosporum. The ascopirone Ti, the dehydrated form of ascopirone T; Ascopirone T2 and T3, the monohydrated tautomeric form of ascopirone T. Ascopirone M can be produced from 1,5-anhydro-D-fructose by EDTA-sensitive dehydratases isolated from the Morelas fungi, such as Morchella vulgaris, Gyromitres , pezizes, such as Peziza echinospora.

Ascopirone M, P and T can also be produced by the treatment of 1,5-anhydro-D-fructose with an alkali under moderate conditions (Ahmand, T., 1995). Preferably, the compound of the present invention is prepared by chemical means or enzymatic means. When the compound of the present invention is prepared by chemical means, it can be prepared according to one of the following methods 1. Ascopirone P can be produced by treating 1,5-anhydro-D fructose with non-aqueous acid at elevated temperature, for example at 70 ° C. 2. Ascopyrones (eg, ascopirone P, T and M) can be produced from 1,5-anhydro-D-fructose by alkaline treatment in accordance with T. Ahmad (Studies on the degradation of some pentoses and of 1, 5-anhydro-D-fructose, the product of the starch-degrading enzyme a-1, 4-glucan lyase, Thesis, The Swedish University of Agricultural Sciences, Sweden, 1995). The structures of all the ascopiruses produced were confirmed by NMR techniques. Preferably, the compound of the present invention is prepared by enzymatic means as described in [3]. For example, ascopyrones (such as, ascopyrone P, T, and M) can be produced from 1,5-anhydro-D-fructose using enzymatic methods as described in [3].

When the compound of the present invention is prepared from 1,5-anhydro-D-fructose preferably 1,5-anhydro-D-fructose is prepared by a method comprising treating an a-1,4-glucan with a a-1, 4-glucan lyase enzyme characterized in that the enzyme is used in substantially pure form. Preferably, the anti-oxidant further comprises a compound selected from carotenes, including β-carotene, tocopherols, ascorbic acid, EDTA, derivatives and mixtures thereof. Preferably, the anti-oxidant further comprises a compound selected from EDTA, citric acid. Preferably, the anti-browning agent further comprises a compound selected from chelators, acidulants, derivatives and mixtures thereof. Preferably, the acidulants are selected from sulfites, EDTA, citric acid, derivatives and mixtures thereof. Preferably, the anti-browning agent is at a pH of 2 to 7. Preferably, the derivative of the compound of formula I is an ester. The term "ester" includes mono-, di-, tri-, and poly-esters. Preferably, the derivative of the compound of formula I is an ester wherein an ester bond is formed from the -OH group of the R3 substituent. In this aspect preferably the derivative of the substituent R3 is a group of formula - (CH2) n-OC (O) - (CH2) pCH3, wherein n and p are independently from each other from 1 to 24, preferably from 1 to 20, preferably from 1 to 10, preferably 1 to 5, or preferably 1, 2, or 3. In yet another preferred embodiment the derivative of the substituent R3 is a group of the formula - (CH2) n-OC (OHCH2) pCH3, wherein is from 1 to 24, preferably from 1 to 20, op is from 1 to 10, op is from 1 to 5, on = 1, 2, or 3. Preferably, the derivative of the compound of formula I is an ester wherein the substituent R1 and / or R2 is an OH group and wherein the ester linkage is formed from the OH group of the substituent R1 and / or substituent R2. In this aspect preferably the derivative of the substituent R1 and / or substituent R2 is a group of the formula - (CH2) n-OC (0) - (CH2) PCH3, wherein n and p are independently from each other from 1 to 24, preferably from 1 to 20, preferably from 1 to 10, preferably from 1 to 5, or preferably 1, 2, or 3. In still another preferred embodiment the derivative of the substituent R 1 and / or the substituent R2 is a group of the formula - (CH2) -OC (0) - (CH2) pCH3, wherein p is from 1 to 24, preferably from 1 to 20, op is from 1 to 10, op is from 1 to 5, on = 1, 2, or 3. In a preferred aspect the compound of formula I is a diester where it is a substituent R1 is a -OH group and where the ester linkages are formed from the -OH group of the substituent R4 and from the group -OH of the substituent R3 In a highly preferred aspect the compound of formula I is a compound of the formula This compound (3,6-di-0-acetyl-1,5-anhydro-4-deoxy-D-glycero-hex-3-enopyranose-2ulose) can be prepared according to the teachings of Andersen et al. (1998), "Structure of 1, 5-anhydro-D-fructose: X-ray analysis of crystalline acetylated dimeric forms, J. Carbohydr, Chem. 17: 1027-1035". The aspect of the present invention wherein the derivative of the compound of formula I is an ester is particularly preferred because the compound can be lipophilic and / or can have both lipophilic and lipophobic properties. When the compound has both lipophilic and lipophobic properties the compound easily resides in an interface of a water / oil emulsion. The residence of the compound in an interface of a water / oil emulsion may allow it to act as an emulsifier. Therefore, the present invention can additionally provide compounds having a dual functional effect. The compounds can act as both an antioxidant and an emulsifier. The emulsifying properties of the compounds according to the present invention were measured in Example 6. Preferably, the plant or fungal material is a material from plants or fungi selected from carrots, peas, beans, potatoes, cauliflower, bananas. , apples, pears, apricots, grapes, raisins, strawberries, apples and mushrooms. The invention will now be described, by way of example only, with reference to the accompanying drawings in which: Figure 1 illustrates the present invention. Figure 2 illustrates the present invention. Figure 3 illustrates the present invention. Figure 4 illustrates the present invention.

EXAMPLES Synthesis General procedures The melting points were determined with a melting point apparatus (Büchi 510) and corrected. Optical rotations were measured on a Perkin-Elmer 241 polarimeter by the Department of Organic Chemistry, Technical University of Denmark (Department of Organic Chemistry, Technical University of Denmark). The 1 H NMR and 13 C NMR spectra were recorded with a Varian Gemini instrument 200 MHz (room temperature) and a Bruker AC 300 instrument (room temperature). For NMR spectra, the peak of the solvent was used as a reference. The microanalyses were carried out by the Chemical Laboratory II (Chemical Laboratory II) University of Copenhagen. The progress of all the reactions was monitored by thin layer chromatography using aluminum foils precoated with silica gel 60 F254 with a thickness of 0.2 mm. The compounds were detected with UV light (254 nm) and / or by spraying the sheets with 1.5% ammonium molybdiconate solution, 1% cerium sulfate and 10% sulfuric acid, followed by heating. The column chromatography was conducted under pressure (1.98 atmospheres) with silica gel (0.043-0.063 mm). 3. 4,6-Tri-0-acetyl-1,5-anhydro-D-fructose oxime (2) [literature = F.W. Lichtenthaler and P. Jarglis. Tetrahedron Letters 21 (1980) 1425-1428] To a solution of 2,3,4,6-tetra-0-acetyl-2-hydroxy-D-glucan (7.90 g, 23.9 mmol) in dry pyridine (40 mL, 496 mmol) , HONH2, HCl (5.85 g, 84.2 mmol) were added and the mixture was stirred for 24 hours. The reaction mixture was concentrated and dissolved in CHCl3 (300 mL). The organic phase was washed with 1 M HCl (aqueous, 75 mL), saturated aqueous NaHC 3 (75 mL) and H20 (75 mL), dried (MgSO-t) and evaporated to a syrup of 2, (7.19 g, 99%). By adding a small volume of EtOH the product crystallized (4.43 g, 61%, mp 86-89 ° C). Two recrystallizations from toluene allowed an analytical sample: mp 90-92 ° C; [a] -39.4 ° C (c 1.3, CHCl3) [pf of the literature 89-90 ° C, [a] D-39.0 ° C (c 0.4, CHCI3)]. 1 H NMR (DMSO-d 6 at 2.49, 300 MHz) d 1.99 (s, 3 H, OCOCH 3) 2.02 (s, 3H, OCOCH3), 2.03 (s, 3H, OCOCH3), 3.87 (ddd, J = 3.0, 5.5 and 8.5, 1 H, H-5), 4.03 (d.J = 15.0, 1 H, H-1), 4.05 (dd, J = 3.0 and 12.0, 1 H, H-6), 4.12 (dd, J = 5.5 and 12.0, 1 H, H-6 '), 4.88 (d, J = 15.0, 1 H, H-1'), 4.93 (dd, J = 8.0 and 9.0, 1 H, H-4), 5.54 (d.J = 8.0) , 1 H, H-3), 11.42 (s, 1 H, NOH). 13 C NMR (DMSO-d6 at 39.6, 50.3 MHz) d 20.6 (3 x OCOCH 3), 60.9 (C-1), 62.5 (C-6), 69.3 (C-4), 70.5 (C-3), 74.9 ( C-5), 148.9 (C-2), 169.3-170.2 (3 x OCOCH3). Analytical calculation for: C? 2H? 7N08: C, 47.53; H, 5.65; N, 4.62.

Found: C, 47.57; H, 5.56; N, 4.50. 3. 4.6-Tri-0-acetyl-1.5-anhydro-D-fructose (3) [literature = P. Jarglis, Thesis, Darmstadt-Eberstadt 1980] 3,4,6-Tri-O-acetyl-1,5-anhydro- D-fructose oxime (2) (5.00 g, 16.5 mmol) was dissolved in dioxane (100 mL) and NH4OAc (13.0 g, 169 mmol) was added. The mixture was cooled on ice, 15% TiC (44 mL, 54 mmol) was added and the reaction mixture was stirred at room temperature for 3 hours. The mixture was extracted with CHCl3 (5 x 30 mL) and the organic phases were combined and washed with saturated aqueous NaHCO3 (70 + 50 mL). The combined aqueous phases were extracted with CHCl3 (30 mL) and the combined organic phase was washed with H20 (30 mL). The organic phase was dried (MgSO-i) and evaporated to a syrup of 3, (3.54 g, 75%). After the addition of Et20 the product crystallized (1.29 g, mp 81-85 ° C). Two recrystallizations from Et20 allowed obtaining an analytical sample: mp 93-95 ° C; [a] D-7.2 ° C (c 1.5, CHCI3) [pf from the literature 86-88 ° C, [a] D-10 (c 0.5, CHCI3)]. 1 H NMR (CDCl 3 at 7.27, 300 MHz) d 2.08 (s, 3 H, OCOCH 3), 2.10 (s, 3 H, OCOCH 3), 2.16 (s, 3 H, OCOCH 3), 3.99 (ddd, J = 2.5, 5.0 and 9.0, 1 H, H-5), 4.10 (d, J = 15.5, 1 H, H-1), 4.23 (dd, J = 2.5 and 12.5, 1 H, H-6), 4.27 (d, J = 15.5, 1 H, H-1 '), 4.32 (dd, J = 5.0 and 12.5.1 H, H-6'), 5.34 (t, J = 9.5, 1 H, H-4), 5.42 (d, J = 10. 0, 1 H, H-3). 13 C NMR (CDCl 3 at 77.0, 75.5 MHz) d 20.4, 20.7 (3 x 0C0CH3), 62.1 (C-6), 69.4 (C-4), 72.9 (C-1), 76.5 (C-5), 76.8 (C-3), 169.1, 169.8, 170.5 (3 x OCOCH3), 196.3 (C-2). Analytical calculation for: C, 50.00; H, 5.59. Found: C, 49. 87; H, 5.56. 3. 6-Di-O-acetyl-1,5-anhydro-D-glycero-hex-3-en-2-ulose (4) [literature = S. Andersen et al. J. Carbohydrate Chemistry, 17 (1998) 1027-1035, P. Jargiis and F.W. Lichtenthaler Angrew. Chem. 94 (1982) 140-141 with a benzocylated analogue]. To a solution of 3,4,6-tri-0-acetyl-1,5-anhydro-D-fructose (3) (2.21 g, 7.67 mmol) in dry acetone (77 mL), anhydrous NaOAc (2.2 g) was added. ) and the reaction mixture was stirred for 3 hours. The salts were filtered and washed with acetone. The filtrate was concentrated and purified by column chromatography (30 g of silica, eluted with hexane-EtOAc, 2: 1) to give 4 as a syrup (1.56 g, 89%): 1 H NMR (CDCl 3 at 7.27, 300 MHz ) d 2.12 (s, 3H, OCOCH3), 2.26 (s, 3H, OCOCH3), 4.24 (dd, J = 4.0 and 12.0, 1 H, H-6), 4.25 (dd, J = 2.0 and 16.5, 1 H , H-1), 4.42 (dd, J = 6.0 and 12.0, 1 H, H-6 '), 4.46 (d, J = 16.5, 1 H, H-1'), 4. 80 (dddd, J = 2.0, 2.0, 4.0 and 6. 0, 1 H, H-5), 6.59 (d, J = 2. 0, 1 H, H-4). 13 C NMR (CDCl 3 at 77.0, 50.3 MHz) d 20.3-20.7 (2 x OCOCH 3), 64.4 (C-6), 71.4 (C-1), 72.6 (C-5), 132.8 (C-4), 143.8 ( C-3), 168.1-170.7 (2 x OCOCH3), 187.7 (C-2).

Analytical calculation for C? 0H? 2O6: C, 52.63; H, 5.30. Found: C, 52.01; H, 5.18. 1. 5-Anhydro-G-glycero-hexo-2,3-diulose (5) (Ascopirone T v M) A 3,6-Di-0-acetyl-1,5-anhydro-D-glycero-hex-3-en -2-ulosa (4) (2.89 g, 13.1 mmol) was added 4M aqueous HCl (130 mL) and the reaction mixture was stirred for 24 hours. The mixture was concentrated and co-concentrated with H20 (2 x 60 mL) to a syrup, which was purified by chromatography (60 g of silica, eluted with EtOAc, then with CHC-MeOH, 4: 1) to give 5 g. as an amorphous solid (1.84 g, 97%). 13C NMR of hydrated 5 (D20, MeOH at 49.5 ppm, 50.3 MHz) d 37.4 (C-4), 64.2 (C-6), 70.9 (C-1), 76.4 (C-5), 92.9 (C-3) ), 93.9 (C-2). 1, 5-Anhydro-D-glycero-hex-1-en-3-ulose (6) (Ascopirone P) [Literature = F. Shafizadeh et al. Carbohyd. Res. 67 (1978) 433-447] 1,5-Anhydro-D-glycero-hexo-2,3-diulose (5) (1.04 g, 7.2 mmol) was dissolved in dry pyridine (100 mL) and an 4 A molecular sieve (10.8 g). The mixture was heated to 120 ° C in an N2 atmosphere for 1 hour and concentrated in vacuo to give a syrup. The syrup was dissolved in H20 (50 mL) and 1 M HCl was added until it reached pH 4-5. The aqueous phase was extracted with EtOAc (5 x 100 mL) and the combined organic phases were dried (MgSO-i) and evaporated to a brown syrup. After the addition of EtOAc / hexane, 6 crystallized (0.1896 g, 18%, mp 90-95 ° C) [pf of the literature 98.5-99 ° C]. The mother liquor was purified by chromatography (20 g, silica, eluted with EtOAc, then with CHC-MeOH, 4: 1) to obtain 5 (0.57 g) and 6 (0.0494 g). Total yield of 6: 23% (51% when the starting material is recovered by subtraction). 1 H NMR (D 20, MeOH at 3.34 ppm, 300 MHz) d 2.53 (dd, J = 3.5 and 17.5, 1 H, H-4), 2.87 (dd, J = 14.5 and 17.5, 1 H, H-4 ') , 3.79 (dd, J = 5.5 and 12.5, 1 H, H-6), 3.88 (dd, J = 3.0 and 12.5, 1 H, H-6 '), 4.57 (m, 1 H, H-5), 7.53 (s, 1 H, H-1). 13 C NMR (D 20, MeOH at 49.5 ppm, 75.5 MHz) d 37.7 (C-4), 63.7 (C-6), 81.0 (C-5), 136.1 (C-2), 152.3 (C-1) , 192.9 (C-3). Evaluation The following five methods were used to evaluate the compounds according to the present invention. Each of the tests shows that the compounds are effective anti-oxidants and / or anti-darkening agents. 1.- The thiobarbutyric acid (TBA) method was used to measure substrates reactive to thiobarbutyric acid (TBARS), such as MDA (malodialdehyde), etc. 2.- The lipid peroxidation method (LPO) was used to measure MDA and 4-HNE (4h-hydroxynonenal). Note: Both MDA and 4-HNE are the products of oxidation of polyunsaturated fatty acids from lipids. 3.- The ß-carotene method was used to measure the protection of the oxidation of ß-carotene by the lipid peroxide in the presence of an added anti-oxidant. 4. The method of DPPH (1,1-diphenyl-2-picrylhydrazyl) was used to measure the radical elimination activity of an anti-oxidant towards the DPPH radical. 5.- The polyphenol oxidase (PPO) method was used to measure the inhibition of polyphenol oxidase in vegetables, fruits and fungi.

EXAMPLE 1 The compounds of the present invention were investigated as an anti-browning agent in vegetable and fruit products. Figure 1 shows the effect of ascopirones and kojic acid to prevent darkening of apple slices. After a prolonged period, for example weeks or months, at room temperature it was apparent that ascopirone and kojic acid were able to completely prevent darkening. In contrast, ascorbic acid was unable to do so (photo not shown). Figure 2 shows that PPO, the enzyme that is responsible for darkening, is inhibited by the compounds of the present invention such as ascopirone and kojic acid.

EXAMPLE 2 Principle and objective: PPO is one of the enzymes involved in the oxidative darkening of vegetables and fruits. An efficient inhibitor is needed that inhibits the enzyme and therefore prevents darkening and oxidation. The inventors found that Ascopirone P (APP) is an efficient inhibitor for this purpose (see figure 2 and table 1).

Test conditions: White: To 20 μl of PPO (20 units, from fungus, product Sigma, EC 1.14.18.1), 0.45 ml of water, 0.43 ml of phosphate buffer (Na2HP04-Na2H2P? 4 0.2 M) were added. , pH 6.5), so that the final volume was 0.9 ml. Control: To 20 μl of PPO were added 0.15 ml of water, 0.43 ml of phosphate buffer (Na2HP04-Na2H2P04 0.2 M, pH 6.5), then 0.3 ml of tyrosine (BDH product, 1 mM). During the running time the progress of the reaction was monitored at room temperature (24 ° C) at 475 nm when using a Perkin Elmer UV / VIS Lambda 18 spectrometer. Test: To 20 μl of PPO was added 0.143 ml of water, 7 μl of APP (final concentration 10 ppm), 0.430 ml of phosphate buffer (Na2HPO4-Na2H2PO40.2 M, pH 6.5), then 0.3 ml of tyrosine (BDH product, 1 mM). The time of progress of the reaction was monitored as mentioned above.

The results obtained are shown in Table 1 and Figure 2. Figure 2 shows the inhibition of ascopirone P (APP) on fungal polyphenol oxidase (PPO).

TABLE 1 Inhibition of 10 ppm of APP on polyphenol oxidase (PPO) as indicated by the very slow increase in absorbance at 475 nm compared to the control. Values above OD 475 nm indicate more darkening product formation.

EXAMPLE 3 Principle and objective: Carotenoids are some of the pigments that can be used to give a healthy color to food and beverages. Therefore they are used as food colorants. Β-carotene is also a precursor of vitamin A. Carotene molecules are highly saturated and are prone to oxidative degradation; which is stimulated by light, enzymes, metals, and co-oxidation with lipid hydroperoxides. In the system used, beta-carotene is exposed to oxygen and the oxidative intermediates of linoleic acid. The results indicated that the presence of APP in said system delays the oxidative de-coloration of beta-carotene.

Assay conditions: The assay was carried out in accordance with H. E. Miller (JAOSC (1970) 48: 91). The test system consisted of beta-carotene, linoleic acid, and Tween 40. In the blank, no anti-oxidant was used, while in the tests, either APP in a concentration of 2.5-25 ppm or ascorbate were added. sodium at a concentration of 100-500 ppm. The mixtures were incubated in the dark for the time and at the indicated temperature (see Table 2.1 and 2.2). The absorbance was then measured at 470 nm.

The absorbance provided an indication of the beta-carotene content. Lower values of OD 470 nm indicate further degradation of beta-carotene.

TABLE 2.1 Effect of APP and sodium ascorbate to prevent discoloration of beta-carotene by oxygen and oxidative intermediates of linoleic acid after incubation at 37 ° C for 161 minutes in the dark.

TABLE 2.2 Effect of APP and sodium ascorbate to prevent the de-staining of beta-carotene by oxygen and oxidative intermediates of linoleic acid after an incubation time at 37 ° C for 161 minutes in the dark at 24 ° C for 17.5 hours in the darkness.

These data are illustrated in Figure 3. Figure 3 shows the effect of APP to prevent oxidative degradation and de-coloration of beta-carotene. Figure 3 shows that the compounds of the present invention such as APP can be about 100 times as effective as ascorbic acid in preventing the de-staining of β-carotene.

EXAMPLE 4 Principle and objective: A major area for the use of anti-oxidants in food-related products is their ability to prevent the oxidation of polyunsaturated fatty acids in lipids. Oxidation of lipids and fatty acids is a major problem in foods. The inventors have found that APP, similarly to the other anti-oxidants, such as sodium ascorbate, was able to delay the oxidation of linoleic acid, since in the presence of APP the products of oxidative degradation of malonaldehyde (MDA) and 4-hydroxynonenal (4HNE) was much smaller than the control (in which no antioxidant was added). Test conditions: The MDA and 4HNE assay was carried out by the LPO method, using the test equipment from OXIS International, Inc. (Portland, OR, USA) and in accordance with its protocol. The assay mixture for the blank contained linoleic acid and Tween 40. For the assays, APP or sodium ascorbate was added. After incubation at 24 ° C in the dark for 10 days, the samples were tested for the contents of MDA and 4HNE as indicated by their absorbance at 586 nm as given in Table 3. Values greater than OD of 586 nm indicated higher content of MDA and 4HNE, and therefore more degradation of linoleic acid.

TABLE 3 APP delays the production of MDA and 4HNE from linoleic acid.

These data are illustrated in Figure 4. Figure 4 shows the effect of APP on the delay of oxidative degradation of the polyunsaturated fatty acid of linoleic acid. Figure 4 shows the ability of APP to delay the oxidative degradation of linoleic acid. It is observed that 6.2 ppm of APP is almost as efficient as 300 ppm of ascorbic acid.

EXAMPLE 5 - Use of the compound as an anti-oxidant EXAMPLE 5.1 - Use of the compound as an anti-oxidant in a 50% mayonnaise A 50% mayonnaise is used for salads, open sandwiches, etc. both in the food service branch and in the retail sale. The low oil content of 50% mayonnaise makes it suitable for low calorie applications. A typical composition of mayonnaise is as follows: Soybean oil 50.0% Tarragon vinegar 4.0% Egg yolk 3.5% Sugar 3.0% Salt 1.0% Potassium sorbate 0.1% Water 35.2% MAYODAN 602 3.0% Lemon flavor 10251 0.2% MAYODAN 602 ensures a fine, stable oil dispersion and the required viscosity, therefore providing a mayonnaise to the 50% with a long shelf life. The flavor 10251 is a natural lemon flavoring that provides mayonnaise with the fresh flavor of lemon. Mayonnaise is typically prepared by the following method: 1) Dry mix the MAYODAN 602, sugar and salt. Spread the oil in a ratio of 1 part powder to 2 parts oil. 2) Add the flavor and potassium sorbate to the water and pour into the Koruma mixer. Add 1) 3) Add the egg yolk. 4) Add the oil continuously in vacuum. 5) After 2/3 of the oil has been added (slowly), mix the tarragon vinegar with the remaining 1/3 of the oil, and add. When the compound of the present invention is added to mayonnaise as an anti-oxidant the results are comparable to those of the food antioxidants GRINDOX 142 and GRINDOX 1029.

GRINDOX 142: Ascorbyl palmitate 10% Propyl gallate 20% Citric acid 10% Food grade emulsifier 60% Form at 25 ° C paste Color gray to pale brown Density 1.1 g / ml (All percentages are by weight) GRINDOX 1029: Ascorbyl palmitate 20% Natural tocopherols 20% Food grade emulsifier 60% Form at 25 ° C paste Light brown color Density 1.0 g / ml (All percentages are by weight) In the test procedure the anti-oxidant compounds were added to the mayonnaise to provide an anti-oxidant concentration in the order of about 500 ppm. Then the mayonnaise was placed in a calorimetric bomb at a temperature of 80 ° C containing pure O2.

An induction of the period of the initiation of substantial oxidation of the product is then measured. The results show that the compounds of the present invention are excellent food antioxidants and are comparable with the anti-oxidants of known food products GRINDOX 142 or GRINDOX 1029.

EXAMPLE 5.2 - Use of the compounds as an anti-oxidant in a yogurt salad dressing with 50% oil The dressing of yogurt for salad with 50% oil is used for salads, potatoes, raw vegetable salads, meat, fish and boiled vegetables. Composition: Soybean oil 50.0% Yogurt (simple) 39.0% Vinegar (10%) 3.5% Sugar 3.0% Egg yolk 2.0% Salt 1.0% Potassium sorbate 0.1% MAYODAN 525 1.4% Flavoring that masks the acidity 2072 0.02% The MAYODAN 525 provides unique stability to the emulsion, prevents syneresis, ensures uniform oil dispersion and viscosity, improves tolerance to production procedures and ensures a long shelf life. The flavoring 2072 is a flavor identical to the natural one, which masks the acid and reduces the acidified flavor of the dressing without affecting the pH value. Procedure: 1) Mix dry MAYODAN 525, sugar and salt. Spread the oil in a ratio of 1 part powder to 2 parts oil. 2) Introduce the flavoring, potassium sorbate and yogurt into the Koruma mixer. Add 1) 3) Add the egg yolk. 4) Add the oil continuously in vacuum. 5) After 2/3 of the oil has been added (slowly), mix the vinegar with the remaining 1/3 of the oil, and add. 6) Add spices if required. The compositions were evaluated as described above. The results show that the compounds of the present invention are excellent food antioxidants.

EXAMPLE 6 - Emulsifying properties Testing the compound of interest as an emulsifier in a water / oil emulsifier Materials: 1) 83.4% soybean oil (84 ml) 16.6% water (16.6 g) 2) 83.4% soybean oil (84) ml) 16.2% water (16.2 g) 0.4% GRINDSTED® CITREM BC (0.4 g) 3) 83.4% soybean oil (84 ml) 16.2% water (16.2 g) 0.4% DIMODAN® PVP ( 0.4 g) 4) 83.4% soybean oil (84 ml) 16.2% water (16.2 g) 0.4% COMPOUND OF INTEREST (0.4 g) Methods: 1. The oil is heated to 60 ° C 2. 84 ml of soybean oil (with or without emulsifier) are weighed in a cup and then stirred (Heidolph, speed 2.5) in a water bath at 60 ° C. 3. The heavy amount of distilled water (pH 4.7) is added to the oil while stirring. Stirring is continued for 20 minutes, and the emulsion is maintained at 60 ° C.

Right after the emulsification, a sample of the emulsion is studied under a microscope. The rest of the emulsion will be seen inside a cup that is placed at room temperature. Follow the separation of the water and possibly the oil after some time.

Results * Photographs from microscopy to continue. ** Previous time approximately 15 ml of water will be separated from the emulsion Conclusions The compound of interest acts as a water / oil emulsifier. The emulsification properties of Col evaluated as the ability to create small drops of water - they are close to GRINDSTED® CITREM BS and are better than DIMODAN® PVP. The emusification with the Col is considerably more stable than the non-emulsified control. GRINDSTED® CITREM BS is a mixture of citric acid ester / monoglyceride. DIMODAN® PVP is distilled monoglyceride. All publications mentioned in the aforementioned specification are incorporated herein by reference. Various modifications and variations of the methods described and the system of the invention will be apparent to those skilled in the art without departing from the scope and spirit of the invention. Although the invention has been described in connection with the preferred embodiments, it should be understood that the invention as claimed should not be unduly limited to said specific modalities. In fact, it is intended that various modifications of the modes described to carry out the invention which are obvious to those skilled in chemistry or related areas are within the scope of the following claims.

References [1] Shafizadeh, F., Furneaux R.H., Stevenson. T.T. and Cochran, T. G. 1, 5 anhydro-4-deoxy-D-glycero-hex-1-en-3-ulose and other pyrolysis products of cellulose. Carbohydr. Res. 67 (1978): 433-447. [2] Stevenson, T.T., Stenkmap, R.E., Jensen, L.H., Cochran, T.T., Shafizadeh, F., and Furneaux R.H. The crystal structure of 1, 5-anhydro-4-deoxy-D-glycero-hex-1-en-3-ulose. Carbohydr. Res. 90 (1981): 319-325. [3] M.-A Baute, G. Deffieux, J. Vercauteren, R. Baute, and A. Badoc. Enzymatic activity degrading 1, 4-a-gIucans to Ascopyrones P and T in Pezizales ad Tuberales. Phytochemistry, 33 (1991): 41-45. [4] T. Ahmad, Studies on the degradation of some pentoses and of 1, 5-anhydro-D-f rucióse, the product of the starch-degrading enzyme a-1,4-glucan lyase. PhD Thesis, The Swedish University of Agricultural Sciences, Sweden, 1995.

Claims (18)

NOVELTY OF THE INVENTION CLAIMS

1. - An anti-oxidant composition characterized in that it comprises a cyclic compound having the formula I Formula I or a derivative thereof, wherein R1 and R2 are independently selected from -OH, = O, where R3 is a substituent comprising a -OH group; and where R4 and R5 are different from H; with the proviso that the compound is different from ascorbic acid.

2. A process for the prevention and / or reduction of oxidation of a material, characterized in that it comprises the step of contacting the material with a cyclic compound having the formula I Formula I or a derivative thereof, wherein R1 and R2 are independently selected from -OH, = O, where R3 is a substituent comprising a -OH group; and where R4 and R5 are different from H; with the proviso that the compound is different from ascorbic acid.

3. The use of a compound for the prevention and / or reduction of oxidation of a material, wherein the compound is a cyclic compound having the formula I Formula I or a derivative thereof, wherein R1 and R2 are independently selected from -OH, = O, where R3 is a substituent comprising a -OH group; and where R4 and R5 are different from H; with the proviso that the compound is different from ascorbic acid.

4. An anti-darkening composition characterized in that it comprises a cyclic compound having the formula I Formula I or a derivative thereof, wherein R1 and R2 are independently selected from -OH, = O, where R3 is a substituent comprising a -OH group; and where R4 and R5 are different from H; with the proviso that the compound is different from ascorbic acid.

5. - A method for the prevention and / or reduction of the darkening of a plant or fungal material, characterized in that it comprises the step of contacting the plant or fungal material with a cyclic compound having the formula I Formula I or a derivative thereof, wherein R1 and R2 are independently selected from -OH, = 0, where R3 is a substituent comprising a -OH group; and where R4 and R5 are different from H; with the proviso that the compound is different from ascorbic acid.

6. The use of a compound for the prevention and / or reduction of the obscuration of a plant or fungal material, wherein the compound is a cyclic compound having the formula I Formula I or a derivative thereof, wherein R1 and R2 are independently selected from -OH, = O, where R3 is a substituent comprising a -OH group; and where R4 and R5 are different from H; with the proviso that the compound is different from ascorbic acid.

7. - The invention according to any of the preceding claims, further characterized in that the cyclic compound is a compound having the Formula II Formula II or a derivative thereof; wherein R1, R2, R3, R4, and R5 are as defined in the preceding claims.

8. The invention according to any of the preceding claims, further characterized in that the cyclic compound is a compound having Formula III Formula III or a derivative thereof; wherein R1, R2, R3, R4, and R5 are as defined in the preceding claims.

9. The invention according to any of the preceding claims, further characterized in that R3 is or comprises a CH2OH group.

10. The invention according to any of the preceding claims, further characterized in that R4 and R5 are independently selected from -OH, = 0 or represent a bond with an adjacent atom in the ring of the cyclic compound.

11. The invention according to any of the preceding claims, further characterized in that the cyclic compound comprises a ring of five or six members.

12. The invention according to any of the preceding claims, further characterized in that the compound is selected from Ascopirone M, Ascopirone P, Ascopirone T, Ascopirone T-i, Ascopirone T2, kojic acid, and mixtures thereof.

13. The invention according to any of the preceding claims, further characterized in that the anti-oxidant composition comprises a compound selected from tocopherols, ascorbic acid, EDTA, derivatives and mixtures thereof.

14. The invention according to any of the preceding claims, further characterized in that the anti-darkening composition additionally comprises a compound selected from chelators, acidulants, derivatives and mixtures thereof.

15. The invention according to claim 14, further characterized in that the acidulants are selected from sulfites, EDTA, citric acid, derivatives and mixtures thereof.

16. A process for the preparation of a cyclic compound having the Formula I for use in the invention as claimed in any of the preceding claims, characterized in that the compound is prepared by chemical methods.

17. A process for the preparation of a cyclic compound having the Formula I for use in the invention as claimed in any of the preceding claims, further characterized in that the compound is prepared by enzymatic methods.

18. The invention according to any of the preceding claims, further characterized in that the derivative of the compound of Formula I is an ester.