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WO2012169661A1 - Cristal de sel métallique polyvalent de monatine - Google Patents

Cristal de sel métallique polyvalent de monatine Download PDF

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Publication number
WO2012169661A1
WO2012169661A1 PCT/JP2012/065176 JP2012065176W WO2012169661A1 WO 2012169661 A1 WO2012169661 A1 WO 2012169661A1 JP 2012065176 W JP2012065176 W JP 2012065176W WO 2012169661 A1 WO2012169661 A1 WO 2012169661A1
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Prior art keywords
monatin
crystals
crystal
polyvalent metal
metal salt
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PCT/JP2012/065176
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English (en)
Japanese (ja)
Inventor
森　健一
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Ajinomoto Co Inc
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Ajinomoto Co Inc
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    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
    • A23L2/00—Non-alcoholic beverages; Dry compositions or concentrates therefor; Preparation or treatment thereof
    • A23L2/52—Adding ingredients
    • A23L2/60—Sweeteners
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
    • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • A23L27/30—Artificial sweetening agents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P1/00—Drugs for disorders of the alimentary tract or the digestive system
    • A61P1/02—Stomatological preparations, e.g. drugs for caries, aphtae, periodontitis
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P3/00—Drugs for disorders of the metabolism
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P3/00—Drugs for disorders of the metabolism
    • A61P3/04—Anorexiants; Antiobesity agents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P3/00—Drugs for disorders of the metabolism
    • A61P3/08—Drugs for disorders of the metabolism for glucose homeostasis
    • A61P3/10—Drugs for disorders of the metabolism for glucose homeostasis for hyperglycaemia, e.g. antidiabetics
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
    • C07D209/18—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D209/20—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals substituted additionally by nitrogen atoms, e.g. tryptophane

Definitions

  • the present invention relates to a novel (2R, 4R) monatin polyvalent metal salt crystal.
  • the present invention also relates to a sweetening composition containing the crystals.
  • the present invention relates to a sweetening composition containing a reducing sugar.
  • Patent Documents 4 to 5 In recent years, several studies have been made on the production method of monatin (Patent Documents 4 to 5), and some findings have been reported on monatin crystals. Examples of polyvalent metal salt crystals and their effects There was no description about.
  • Patent Documents 6 to 10 ZA 87/4288 ZA 88/4220 US 5,994,559 WO2003-056026 WO2003-059865 WO2003-045914 US2005-272939 JP-A-2005-154291 JP 2006-052213 A JP2010-155817A R. Vleggaar et. Al. , J .; Chem. Soc. Perkin Trans. , 3095-3098, (1992) Holzapfel et. al. , Synthetic Communications, 24 (22), 3197-3211 (1994). K. Nakamura et. al. , Organic Letters, 2, 2967-2970 (2000).
  • An object of the present invention is to provide a novel monatin crystal that can form a sweetening composition that hardly decomposes even when exposed to high temperature and high humidity in the presence of reducing sugar.
  • [5] Has intrinsic X-ray diffraction peaks at diffraction angles (2 ⁇ ⁇ 0.2 °, CuK ⁇ ) at 4.9 °, 16.8 °, 18.0 ° and 24.6 ° ((2R, 4R) characterized in that it is a monatin) 2 magnesium salt crystals, [4], wherein the (2R, 4R) monatin polyvalent metal salt crystals.
  • a diffraction angle (2 ⁇ ⁇ 0.2 °, CuK ⁇ ) having a characteristic X-ray diffraction peak of any of the following (1) to (3) ((2R, 4R) monatin) is a 2 magnesium salt crystal.
  • the reducing sugar is dihydroxyacetone, glyceraldehyde, erythrulose, erythrose, threose, ribulose, xylulose, ribose, arabinose, xylose, lyxose, deoxyribose, psicose, fructose, sorbose, tagatose, allose, altrose, glucose, mannose [15]
  • (2R.4R) monatin polyvalent metal salt crystals can form a sweetening composition that is difficult to decompose even when exposed to high temperature and high humidity in the presence of reducing sugar. It has become possible to clarify the utility and various physical properties of these stereoisomers as sweeteners. It has also become possible to provide oral products such as beverages, foods, pharmaceuticals, quasi-drugs, and feeds that contain general-purpose stable and safe monatin polyvalent metal salt crystals. The present invention is naturally applicable to (2S, 4S) monatin.
  • natural monatin exhibits a (2S, 4S) isomer in its three-dimensional structure, but all compounds having the same chemical structural formula are collectively referred to as “monatin”, and therefore, non-natural stereoisomers of monatin.
  • stereoisomers of natural monatin “non-natural monatin”, “(2S, 4R) monatin”, “(2R, 4S) monatin”, “(2R, 4R) monatin” or the like.
  • monatin ((2S, 4S) form) is added to these stereoisomers, and these are referred to as “four kinds of stereoisomers”, or natural monatin is particularly referred to as “(2S, 4S) monatin”. Alternatively, it is referred to as “(2S, 4S) monatin” or the like.
  • (2R, 4R) monatin used in the present invention can be prepared by a known method, and its production method is not limited. For example, it can be obtained from tryptophan via indolepyruvic acid by an enzymatic method (Patent Document 4; WO2003-056026), or it can be obtained from tryptophan via indolepyruvic acid via an oxime body (reduction) Patent Document 5; WO2003-059865).
  • (2R, 4R) monatin natural monatin (2S, 4S) isomers, non-natural stereoisomers (2S, 4R) isomers, (2R, 4S) isomers are included. It doesn't matter.
  • divalent metal salts are preferable, alkaline earth metal salts are more preferable, magnesium salts, calcium salts, strontium salts, and barium salts are more preferable, magnesium salts, calcium salts, and barium salts are still more preferable, magnesium salts, calcium A salt is particularly preferred.
  • inorganic polyvalent metal compounds such as calcium hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium acetate, magnesium acetate, calcium oxalate It can be introduced by various methods such as neutralization and salt exchange with organic polyvalent metal compounds such as magnesium oxalate, calcium lactate and magnesium lactate.
  • ((2R, 4R) monatin) 2 divalent metal salt crystals are preferable from the viewpoint of being acceptable for human consumption and easy to prepare.
  • (2R, 4R) monatin) 2 alkaline earth metal salt crystals are more preferred, ((2R, 4R) monatin) 2 magnesium salt crystals, ((2R, 4R) monatin) 2 calcium salt crystals, ((2R, 4R) Monatin 2 strontium salt crystals, ((2R, 4R) monatin) 2 barium salt crystals are more preferred, ((2R, 4R) monatin) 2 magnesium salt crystals, ((2R, 4R) monatin) 2 calcium salt crystals, (( 2R, 4R) monatin) is even more preferably 2 barium salt crystals, ((2R, 4R) monatin) 2 magnesium salt crystals, ((2R 4R) monatin) 2 calcium salt crystals are particularly preferred
  • Crystallization can be obtained by subjecting an aqueous solution containing (2R, 4R) monatin and a calcium source or an organic solvent-containing aqueous solution to standing or stirring crystallization.
  • the (2R, 4R) monatin calcium concentration in the solution is not particularly limited as long as it is supersaturated and crystals are precipitated, but 1 wt% to 60 wt% is preferable. From the viewpoint of obtaining a viscosity of a solution suitable for production, it is more preferably 2 wt% to 50 wt%, further preferably 5 wt% to 45 wt%.
  • the temperature at which the crystals are precipitated is not particularly limited as long as the crystals are precipitated, but is preferably 15 to 100 ° C.
  • Precipitated crystals can be easily obtained wet crystals by subjecting them to a separation step such as a filtration step.
  • the crystal washing is not particularly limited as long as crystal solvent exchange does not occur, but water can be used.
  • a solvent miscible with water such as methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, sec-butanol, propylene glycol, acetonitrile, THF, etc.
  • An inorganic salt or the like may also be included.
  • the wet crystal thus obtained can be converted into a dry crystal by subjecting it to a known drying step.
  • Drying equipment used for drying is not particularly limited, using ((2R, 4R) monatin) temperature range to the extent that 2 calcium salt crystals are not dissolved can be used, vacuum drying or flash drying, hot air drying, etc. it can.
  • 2 calcium salt ((2R, 4R) monatin) of the present invention include those having a crystal polymorphism, depending on the type and crystallization method of crystallization solvent, because it forms a very different crystal forms, on that point or less Detailed description.
  • the melting temperature is not particularly limited as long as the crystals continue to dissolve, but is preferably 15 to 100 ° C.
  • the proportion of ethanol in the ethanol-containing aqueous solution is 50% to 99%, more preferably 75% to 99%.
  • the deposited crystal can be easily obtained by subjecting it to a separation step such as a filtration step.
  • the crystal washing is not particularly limited as long as crystal solvent exchange does not occur, but water can be used.
  • a solvent miscible with water such as methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, sec-butanol, propylene glycol, acetonitrile, THF, etc.
  • the wet crystal thus obtained can be converted into a dry crystal by subjecting it to a known drying step.
  • Drying equipment used for drying is not particularly limited, ((2R, 4R) monatin) the temperature range to the extent that 2 calcium salt crystals are not dissolved can be used, preferably 10 ⁇ 60 ° C., the quality in manufacturing stability From the viewpoint of safety, 10 ° C. to 40 ° C. is more preferable, and vacuum drying, airflow drying, hot air drying, and the like can be used.
  • Crystal precipitation can be obtained by subjecting an isopropanol-containing aqueous solution of (2R, 4R) monatin and calcium source to standing or stirring crystallization.
  • the (2R, 4R) monatin crystal concentration in the solvent is not particularly limited as long as it is supersaturated and crystals are precipitated, but 1 wt% to 60 wt% is preferable. From the viewpoint of obtaining a viscosity of a solution suitable for production, it is more preferably 2 wt% to 50 wt%, further preferably 5 wt% to 45 wt%.
  • the melting temperature is not particularly limited as long as the crystals continue to dissolve, but is preferably 15 to 100 ° C.
  • the proportion of isopropanol in the isopropanol-containing aqueous solution is 50% to 99%, more preferably 75% to 99%.
  • the deposited crystal can be easily obtained by subjecting it to a separation step such as a filtration step.
  • the crystal washing is not particularly limited as long as crystal solvent exchange does not occur, but water can be used.
  • a solvent miscible with water such as methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, sec-butanol, propylene glycol, acetonitrile, THF, etc.
  • the wet crystal thus obtained can be converted into a dry crystal by subjecting it to a known drying step.
  • Drying equipment used for drying is not particularly limited, ((2R, 4R) monatin) the temperature range to the extent that 2 calcium salt crystals are not dissolved can be used, preferably 10 ⁇ 60 ° C., the quality in manufacturing stability From the viewpoint of safety, 10 ° C. to 40 ° C. is more preferable, and vacuum drying, airflow drying, hot air drying, and the like can be used.
  • Crystal precipitation can be obtained by subjecting a THF-containing aqueous solution of (2R, 4R) monatin and a calcium source to standing or stirring crystallization.
  • the (2R, 4R) monatin crystal concentration in the solvent is not particularly limited as long as it is supersaturated and crystals are precipitated, but 1 wt% to 60 wt% is preferable. From the viewpoint of obtaining a viscosity of a solution suitable for production, it is more preferably 2 wt% to 50 wt%, further preferably 5 wt% to 45 wt%.
  • the melting temperature is not particularly limited as long as the crystals continue to dissolve, but is preferably 15 to 100 ° C.
  • the proportion of THF in the aqueous solution containing THF is 50% to 99%, more preferably 75% to 99%.
  • the deposited crystal can be easily obtained by subjecting it to a separation step such as a filtration step.
  • the crystal washing is not particularly limited as long as crystal solvent exchange does not occur, but water can be used.
  • a solvent miscible with water such as methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, sec-butanol, propylene glycol, acetonitrile, THF, etc.
  • the melting temperature is not particularly limited as long as the crystals continue to dissolve, but is preferably 15 to 100 ° C.
  • the proportion of acetonitrile is 50% to 99%, more preferably 75% to 99%.
  • the deposited crystal can be easily obtained by subjecting it to a separation step such as a filtration step.
  • the crystal washing is not particularly limited as long as crystal solvent exchange does not occur, but water can be used.
  • a solvent miscible with water such as methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, sec-butanol, propylene glycol, acetonitrile, THF, etc.
  • An inorganic salt or the like may also be included.
  • the wet crystal thus obtained can be converted into a dry crystal by subjecting it to a known drying step. Drying equipment used for drying is not particularly limited, ((2R, 4R) monatin) the temperature range to the extent that 2 calcium salt crystals are not dissolved can be used, preferably 10 ⁇ 60 ° C., the quality in manufacturing stability From the viewpoint of safety, 10 ° C. to 40 ° C. is more preferable, and vacuum drying, airflow drying, hot air drying, and the like can be used.
  • ((2R, 4R) monatin) 2 calcium salt 5.7 hydrate crystal as shown in FIG. 8, exhibited needles, the diffraction angle (2 ⁇ ⁇ 0.2 °, CuK ⁇ ) As having intrinsic X-ray diffraction peaks at 5.0 °, 12.8 °, 15.3 °, 18.1 ° and 23.7 °. Further, ((2R, 4R) monatin) has a property that it is difficult to decompose even if it is exposed to high temperature and high humidity in the state of coexisting with reducing sugar from a potassium salt crystal.
  • Crystal precipitation can be obtained by subjecting an organic solvent-containing aqueous solution of (2R, 4R) monatin and a calcium source to standing or stirring crystallization.
  • the (2R, 4R) monatin crystal concentration in the solvent is not particularly limited as long as it is supersaturated and crystals are precipitated, but 1 wt% to 60 wt% is preferable. From the viewpoint of obtaining a viscosity of a solution suitable for production, it is more preferably 2 wt% to 50 wt%, further preferably 5 wt% to 45 wt%.
  • the melting temperature is not particularly limited as long as the crystals continue to dissolve, but is preferably 15 to 100 ° C.
  • the type of the organic solvent in the organic solvent-containing aqueous solution is not particularly limited, but is preferably a water-soluble organic solvent having a boiling point of 100 ° C. or lower, and more preferably a water-soluble organic solvent having a boiling point of 80 ° C. or lower.
  • the proportion of the organic solvent is 50% to 99%, more preferably 75% to 99%.
  • organic solvent to be used examples include water-miscible solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, sec-butanol, propylene glycol, and THF.
  • a preferred solvent is ethanol.
  • the deposited crystal can be easily obtained by subjecting it to a separation step such as a filtration step. The crystal washing is not particularly limited as long as crystal solvent exchange does not occur, but water can be used.
  • ((2R, 4R) monatin) 2 calcium salt pentahydrate crystals exhibit needles as shown in FIG. 2, the diffraction angle (2 ⁇ ⁇ 0.2 °, CuK ⁇ ) , 6 It has intrinsic X-ray diffraction peaks at 0.0 °, 9.8 °, 16.0 °, 21.5 °, and 22.3 °. Further, ((2R, 4R) monatin) has a property that it is difficult to decompose even if it is exposed to high temperature and high humidity in the state of coexisting with reducing sugar from a potassium salt crystal. Furthermore ((2R, 4R) monatin) even when exposed to high temperature and high humidity in a state of coexistence with reducing sugars than 2 calcium salt organic solvate crystal also has decomposed hard nature.
  • Crystallization can be obtained by subjecting an aqueous solution containing (2R, 4R) monatin and a magnesium source or an organic solvent-containing aqueous solution to standing or stirring crystallization.
  • the (2R, 4R) monatin magnesium concentration in the solution is not particularly limited as long as it is supersaturated and crystals are precipitated, but 1 wt% to 60 wt% is preferable. From the viewpoint of obtaining a viscosity of a solution suitable for production, it is more preferably 2 wt% to 50 wt%, further preferably 5 wt% to 45 wt%.
  • the temperature at which the crystals are precipitated is not particularly limited as long as the crystals are precipitated, but is preferably 15 to 100 ° C.
  • Precipitated crystals can be easily obtained wet crystals by subjecting them to a separation step such as a filtration step.
  • the crystal washing is not particularly limited as long as crystal solvent exchange does not occur, but water can be used.
  • a solvent miscible with water such as methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, sec-butanol, propylene glycol, acetonitrile, THF, etc.
  • An inorganic salt or the like may also be included.
  • the wet crystal thus obtained can be converted into a dry crystal by subjecting it to a known drying step.
  • Drying equipment used for drying is not particularly limited, using ((2R, 4R) monatin) temperature range enough to 2 magnesium salt crystals are not dissolved can be used, vacuum drying or flash drying, hot air drying, etc. it can.
  • 2 magnesium salt ((2R, 4R) monatin) of the present invention include those having a crystal polymorphism, depending on the type and crystallization method of crystallization solvent, because it forms a very different crystal forms, on that point or less Detailed description.
  • the wet crystal thus obtained can be converted into a dry crystal by subjecting it to a known drying step.
  • Drying equipment used for drying is not particularly limited, ((2R, 4R) monatin) the temperature range to the extent that 2 magnesium salt crystals are not dissolved can be used, preferably 10 ⁇ 60 ° C., the quality in manufacturing stability From the viewpoint of safety, 10 ° C. to 40 ° C. is more preferable, and drying under reduced pressure or airflow drying can be used.
  • the resulting ((2R, 4R) monatin) 2 magnesium salt 3.1 hydrate 2.4 ethanol solvate crystal is thus, as shown in FIG. 18, it exhibited a fine crystal, the diffraction angle (2 ⁇ ⁇ 0. 2 °, CuK ⁇ ) has intrinsic X-ray diffraction peaks at 7.2 °, 10.0 °, 10.6 °, 12.3 °, 14.8 °, 17.8 °, and 25.3 °. Further, ((2R, 4R) monatin) has a property that it is difficult to decompose even if it is exposed to high temperature and high humidity in the state of coexisting with reducing sugar from a potassium salt crystal.
  • Crystal precipitation can be obtained by subjecting a methanol-containing aqueous solution of (2R, 4R) monatin and a magnesium source to standing or stirring crystallization.
  • the (2R, 4R) monatin crystal concentration in the solvent is not particularly limited as long as it is supersaturated and crystals are precipitated, but 1 wt% to 60 wt% is preferable. From the viewpoint of obtaining a viscosity of a solution suitable for production, it is more preferably 2 wt% to 50 wt%, further preferably 5 wt% to 45 wt%.
  • the wet crystal thus obtained can be converted into a dry crystal by subjecting it to a known drying step.
  • Drying equipment used for drying is not particularly limited, ((2R, 4R) monatin) the temperature range to the extent that 2 magnesium salt crystals are not dissolved can be used, preferably 10 ⁇ 60 ° C., the quality in manufacturing stability From the viewpoint of safety, 10 ° C. to 40 ° C. is more preferable, and drying under reduced pressure or airflow drying can be used.
  • Crystal precipitation can be obtained by subjecting a DMF-containing aqueous solution of (2R, 4R) monatin and a magnesium source to standing or stirring crystallization.
  • the (2R, 4R) monatin crystal concentration in the solvent is not particularly limited as long as it is supersaturated and crystals are precipitated, but 1 wt% to 60 wt% is preferable. From the viewpoint of obtaining a viscosity of a solution suitable for production, it is more preferably 2 wt% to 50 wt%, further preferably 5 wt% to 45 wt%.
  • the melting temperature is not particularly limited as long as the crystals continue to dissolve, but is preferably 15 to 100 ° C.
  • the proportion of DMF in the DMF-containing aqueous solution is 50% to 99%, more preferably 75% to 99%.
  • the deposited crystal can be easily obtained by subjecting it to a separation step such as a filtration step.
  • the crystal washing is not particularly limited as long as crystal solvent exchange does not occur, but water can be used.
  • a solvent miscible with water such as methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, sec-butanol, propylene glycol, acetonitrile, THF, etc.
  • the wet crystal thus obtained can be converted into a dry crystal by subjecting it to a known drying step.
  • Drying equipment used for drying is not particularly limited, ((2R, 4R) monatin) the temperature range to the extent that 2 magnesium salt crystals are not dissolved can be used, preferably 10 ⁇ 60 ° C., the quality in manufacturing stability From the viewpoint of safety, 10 ° C. to 40 ° C. is more preferable, and drying under reduced pressure or airflow drying can be used.
  • the inorganic anion concentration mentioned here is a specified number (N) of the salt concentration relative to the total weight (kg).
  • the deposited crystal can be easily obtained by subjecting it to a separation step such as a filtration step.
  • the crystal washing is not particularly limited as long as crystal solvent exchange does not occur, but water can be used.
  • a solvent miscible with water such as methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, sec-butanol, propylene glycol, acetonitrile, THF, etc.
  • An inorganic salt or the like may also be included.
  • the wet crystals thus obtained can be led to dry crystals by controlling the drying conditions.
  • Crystal deposition can be obtained by subjecting an aqueous solution containing (2R, 4R) monatin and a magnesium source or an organic solvent-containing aqueous solution to standing or stirring crystallization.
  • the (2R, 4R) monatin crystal concentration in the solvent is not particularly limited as long as it is supersaturated and crystals are precipitated, but 1 wt% to 60 wt% is preferable. From the viewpoint of obtaining a viscosity of a solution suitable for production, it is more preferably 2 wt% to 50 wt%, further preferably 5 wt% to 45 wt%.
  • the melting temperature is not particularly limited as long as the crystals continue to dissolve, but is preferably 10 to 100 ° C.
  • the temperature of the slurry on which the crystals are precipitated is preferably 10 ° C. to 100 ° C., more preferably 10 ° C. to 65 ° C.
  • the holding time of the slurry liquid is within 24 hours if it is 65 ° C. or higher, and is not particularly limited if it is 65 ° C. or lower.
  • concentration 0.028 N / kg or less is preferable and 0.0069 N / kg or less is more preferable.
  • the inorganic anion concentration mentioned here is a specified number (N) of the salt concentration relative to the total weight (kg).
  • N the number of the salt concentration relative to the total weight (kg).
  • the deposited crystal can be easily obtained by subjecting it to a separation step such as a filtration step.
  • the crystal washing is not particularly limited as long as crystal solvent exchange does not occur, but water can be used.
  • a solvent miscible with water such as methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, sec-butanol, propylene glycol, acetonitrile, THF, etc.
  • An inorganic salt or the like may also be included.
  • the wet crystals thus obtained can be led to dry crystals by controlling the drying conditions at a low temperature.
  • ((2R, 4R) monatin) temperature range enough to 2 magnesium salt crystals are not dissolved can be used, preferably 10 ⁇ 60 ° C., more preferably from 10 ° C. ⁇ 40 ° C. from the viewpoint of quality stability during manufacture, drying time As long as it is not overdried, any time can be selected, and vacuum drying or airflow drying can be used.
  • Crystal precipitation can be obtained by subjecting an organic solvent-containing aqueous solution of (2R, 4R) monatin and a magnesium source to standing or stirring crystallization.
  • the (2R, 4R) monatin crystal concentration in the solvent is not particularly limited as long as it is supersaturated and crystals are precipitated, but 1 wt% to 60 wt% is preferable. From the viewpoint of obtaining a viscosity of a solution suitable for production, it is more preferably 2 wt% to 50 wt%, further preferably 5 wt% to 45 wt%.
  • the melting temperature is not particularly limited as long as the crystals continue to dissolve, but is preferably 15 to 100 ° C.
  • the type of the organic solvent in the organic solvent-containing aqueous solution is not particularly limited, but is preferably a water-soluble organic solvent having a boiling point of 100 ° C. or lower, and more preferably a water-soluble organic solvent having a boiling point of 80 ° C. or lower.
  • the proportion of the organic solvent is 50% to 99%, more preferably 75% to 99%.
  • the deposited crystal can be easily obtained by subjecting it to a separation step such as a filtration step.
  • the crystal washing is not particularly limited as long as crystal solvent exchange does not occur, but water can be used.
  • a solvent miscible with water such as methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, sec-butanol, propylene glycol, acetonitrile, THF, etc.
  • An inorganic salt or the like may also be included.
  • the wet crystals thus obtained can be led to dry crystals by controlling the drying conditions. Drying equipment used for drying is not particularly limited, ((2R, 4R) monatin) the temperature range to the extent that 2 magnesium salt crystals are not dissolved can be used, preferably 25 ⁇ 120 ° C., the quality in manufacturing stability From the viewpoint of safety, 40 ° C. to 100 ° C.
  • desired crystals can be obtained by storing it under high temperature and high humidity.
  • the temperature at that time is 25 ° C. to 100 ° C., more preferably 40 ° C. to 80 ° C.
  • the relative humidity is stored in the range of 20% to 100%, more preferably 60% to 100%.
  • the storage time is 24 hours to 168 hours, more preferably 48 hours to 120 hours.
  • the resulting ((2R, 4R) monatin) 2 magnesium salt tetrahydrate crystals present a fine crystal, the diffraction angle (2 ⁇ ⁇ 0.2 °, CuK ⁇ ) as, 8 It has intrinsic X-ray diffraction peaks at .9 °, 11.2 °, 15.0 °, 17.8 ° and 22.5 °. Further, ((2R, 4R) monatin) has a property that it is difficult to decompose even if it is exposed to high temperature and high humidity in the state of coexisting with reducing sugar from a potassium salt crystal.
  • Crystal deposition can be obtained by subjecting an aqueous solution containing (2R, 4R) monatin and a magnesium source or an organic solvent-containing aqueous solution to standing or stirring crystallization.
  • the (2R, 4R) monatin crystal concentration in the solvent is not particularly limited as long as it is supersaturated and crystals are precipitated, but 1 wt% to 60 wt% is preferable. From the viewpoint of obtaining a viscosity of a solution suitable for production, it is more preferably 2 wt% to 50 wt%, further preferably 5 wt% to 45 wt%.
  • the melting temperature is not particularly limited as long as the crystals continue to dissolve, but is preferably 10 to 100 ° C.
  • the temperature of the slurry on which the crystals are precipitated is preferably 10 ° C. to 100 ° C., more preferably 65 ° C. to 100 ° C.
  • the holding time of the slurry liquid is not particularly limited.
  • the target crystal can be obtained by high-temperature crystallization or a high salting-out effect even at a low temperature.
  • the crystallization temperature is preferably 50 ° C. or higher, more preferably 55 ° C. or higher, still more preferably 60 ° C. or higher, and particularly preferably 65 ° C. or higher.
  • the inorganic anion concentration is preferably 0.14 N / kg or more, more preferably 0.28 N / kg or more, and 0.55 N / kg.
  • the above is more preferable, and 0.88 N / kg or more is particularly preferable.
  • the inorganic anion concentration mentioned here is a specified number (N) of the salt concentration relative to the total weight (kg).
  • the proportion of the organic solvent in the organic solvent-containing aqueous solution is 0.1% to 75%, more preferably 0.1% to 50%.
  • the deposited crystal can be easily obtained by subjecting it to a separation step such as a filtration step.
  • the crystal washing is not particularly limited as long as crystal solvent exchange does not occur, but water can be used.
  • a solvent miscible with water such as methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, sec-butanol, propylene glycol, acetonitrile, THF, etc.
  • An inorganic salt or the like may also be included.
  • the wet crystal thus obtained can be converted into a dry crystal by subjecting it to a known drying step. Drying equipment used for drying is not particularly limited, ((2R, 4R) monatin) temperature range enough to 2 magnesium salt crystals are not dissolved can be used, preferably 10 ⁇ 120 ° C., during production Productivity From the viewpoint, 60 ° C. to 120 ° C. is more preferable, and drying under reduced pressure or airflow drying can be used.
  • ((2R, 4R) monatin) 2 magnesium salt organic solvate crystals have the property of not easily decomposing even when exposed to high temperature and high humidity in the presence of reducing sugar. Furthermore, ((2R, 4R) monatin) 2 magnesium salt tetrahydrate crystal or 7.5 hydrate crystal or 9 hydrate crystal decomposes even when exposed to high temperature and high humidity in the presence of reducing sugar. It also has the most useful properties that are difficult.
  • ((2R, 4R) monatin) Among the two magnesium salt crystals, ((2R, 4R) monatin) 2 magnesium salt 3.1 water from the viewpoint of being stable even if it coexists with a reducing sugar under high temperature and high humidity.
  • the (2R, 4R) monatin polyvalent metal salt crystal of the present invention is slightly different in the ratio of monatin to metal, the ratio of monatin to water, or the ratio of monatin to solvent, as long as it has this peak set. Even if there are fluctuations, they should be regarded as the same crystal.
  • the (2R, 4R) monatin polyvalent metal salt crystal of the present invention can form a monatin crystal together with other inorganic / organic impurities.
  • the lower limit of the chemical purity of the monatin crystal containing the (2R, 4R) monatin polyvalent metal crystal of the present invention is not particularly limited as long as the crystal is formed, but from the viewpoint that a stable crystal can be formed. % By weight is preferred, 60% by weight is more preferred, 70% by weight is more preferred, 80% by weight is even more preferred, 90% by weight is particularly preferred, and 95% by weight is particularly preferred.
  • the upper limit of the chemical purity is preferably 100% by mass from the viewpoint of achieving a sweetness multiplication factor even with a smaller amount.
  • the chemical purity here is the ratio of the “monatin polyvalent metal salt hydrate crystal” mass to the total mass of the monatin crystal.
  • the causes of purity reduction include impurities of monatin itself (including other isomers), inorganic salts, calcium, metal salts other than magnesium, and the like, but are not limited thereto.
  • the (2R, 4R) monatin polyvalent metal salt crystal of the present invention further comprises (2S, 4S) monatin polyvalent metal salt, (2S, 4R) monatin polyvalent metal, (2R, 4S) monatin as other monatin isomers.
  • Monatin crystals can be formed with polyvalent metal salts and other inorganic and organic impurities.
  • the sweetening power of the monatin crystal containing the (2R, 4R) monatin polyvalent metal salt crystal of the present invention is not particularly limited.
  • It is preferably 200 times or more, more preferably 500 times or more, still more preferably 1000 times or more, still more preferably 1500 times or more, still more preferably 2000 times or more, and particularly preferably 2500 times or more with respect to the aqueous sugar solution.
  • the (2R, 4R) monatin polyvalent metal salt crystal of the present invention can be widely used as a sweetening composition.
  • the form of the sweetening composition is not particularly limited, and examples thereof include liquids, powders, and solids.
  • a powder form and a solid form are preferable, and a powder form is particularly preferable.
  • the sweetening composition of the present invention can further contain a reducing sugar.
  • This sweetening composition has the property that monatin is hardly decomposed even when exposed to high temperature and high humidity.
  • the reducing sugar used in the present invention is not particularly limited as long as it is a sugar capable of causing a Maillard reaction having a reducing ability.
  • dihydroxyacetone, glyceraldehyde, erythrulose, erythrose, threose, ribulose Monosaccharides such as xylulose, ribose, arabinose, xylose, lyxose, deoxyribose, psicose, fructose, sorbose, tagatose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, fucose, fucrose, rhamnose, cedoheptulose; And disaccharides such as lactose, maltose, tulanose, sucrose, trehalose, and robiose.
  • Glucose, fructose, maltose, lactose, galactose, mannose, arabinose, and xylose are preferred, glucose, fructose, maltose, and lactose are more preferred, and glucose and maltose are further preferred in terms of good sweetness characteristics and high market needs preferable.
  • the monatin disappearance phenomenon is caused by the Maillard reaction caused by the reducing sugar and the amino group of monatin.
  • the amino group of monatin is sterically covered so that the reducing sugar is difficult to access.
  • the sweetener composition of the present invention can further contain other sweeteners (except for monatin or a salt thereof).
  • Other sweeteners are not particularly limited, and specific examples include oligosaccharides such as fructooligosaccharide, maltooligosaccharide, isomaltoligosaccharide, and galactooligosaccharide; xylitol, lactitol, sorbitol, erythritol, mannitol, maltitol, reduced palatinose -Sugar alcohols such as reduced starch saccharified products; Aspartame, acesulfame K, sucralose, saccharin, stevioside, neotame, cyclamate, stevia, glycyrrhizin, monelin, thaumatin, alitame, dulcin, brazein, neocrine, MHPPAPM (N- [N- [ 3- (3-H
  • aspartame, acesulfame K, sucralose, saccharin, cyclamate, stevioside, neotame are preferred, aspartame, acesulfame K, sucralose, saccharin, stevioside, neotame are more preferred, aspartame, acesulfame K, sucralose, stevioside, Neotame is more preferred, aspartame, acesulfame K, sucralose and neotame are even more preferred, aspartame, acesulfame K and sucralose are particularly preferred, and aspartame and sucralose are particularly preferred.
  • aspartame is particularly preferable from the viewpoint of obtaining a sweet synergistic effect.
  • dextrins such as dextrin, maltodextrin, starch degradation product, reduced starch degradation product, cyclodextrin, indigestible dextrin, polysaccharides such as crystalline cellulose, polydextrose, etc .
  • citric acid PH adjusters such as phosphoric acid, lactic acid, malic acid, tartaric acid, gluconic acid and their salts
  • antioxidants such as L-ascorbic acid, erythorbic acid, tocopherol (vitamin E); sodium acetate, glycine, glycerin
  • Preservatives such as fatty acid esters and lysozyme
  • preservatives such as sodium benzoate and potassium sorbate
  • stabilizers such as pectin, gum arabic, carrageenan, soybean
  • the monatin polyvalent metal salt crystal or sweetening composition of the present invention can be used for oral products such as beverages, foods, pharmaceuticals, quasi drugs, and feeds.
  • the dosage form is not particularly limited, and examples thereof include powder, granules, cubes, pastes, and liquids.
  • liquid drinks such as fruit drinks, vegetable drinks, colas, carbonated drinks, sports drinks, coffee, tea, cocoa, milk drinks; powdered drinks such as powdered juices; plum drinks, medicinal liquors, fruit liquors, sake, etc.
  • Beverages such as liquor; chocolate, cookies, cakes, donuts, chewing gum, jelly, pudding, mousse, Japanese confectionery, etc .; French bread, croissants, etc .; dairy products such as coffee milk, yogurt; ice cream, Ice confectionery such as sherbet; powder mix such as baking mix and dessert mix; tabletop sweetener such as liquid tabletop sweetener and powder tabletop sweetener; seafood dried products and seafood salted products; Processed products; dressing, sauce, soy sauce, miso, mirin, sauce, ketchup, noodle soup Spices such as curry powder; processed cereals such as instant noodles; foods such as cereals; tablet pharmaceuticals; powder pharmaceuticals; syrup pharmaceuticals; drop pharmaceuticals; etc.
  • Quasi-drugs represented by agents, dentifrices, drinks, etc. pet foods, liquid feeds, powdered feeds, etc.
  • beverages, foods, pharmaceuticals, quasi-drugs, and feeds that retain the crystal form of monatin are preferable from the viewpoint of maintaining the sweetness and sweetness stability of monatin, and powdered beverages, confectionery, powder mixes, and powder tabletops.
  • Sweeteners, tablet pharmaceuticals, powdered pharmaceuticals, and powdered feeds are more preferable, and powdered beverages, powdered tabletop sweeteners, and powder mixes are more preferable.
  • the monatin polyvalent metal salt crystal or sweetening composition of the present invention is extremely effective as a metabolic syndrome prevention / treatment agent, obesity prevention / treatment agent, diabetes prevention / treatment agent, and caries prevention agent. In addition, it has sweetness synergistic effect, flavor synergistic effect, bitterness masking, and photodegradation stabilizing effect.
  • TSKguardcolumn SuperIC-C inner diameter 4.6mm, length 10mm ⁇ Eluent> 2.2 mmol / L methanesulfonic acid +1.0 mmol / L 18-crown-6 +0.5 mmol / L histidine ⁇ column temperature> 40 ° C. ⁇ Flow rate> 1 ml / min ⁇ Standard solution> Calcium chloride or magnesium chloride (special grade reagent) was dissolved in pure water to obtain a standard solution.
  • Example 1 ((2R, 4R) monatin) dissolved 2 calcium salt 5 hydrate crystal prepared in Production Example 1 of a (2R, 4R)) monatin potassium salt crystals 5 g (13.7 mmol) in water 75ml At 50 ° C., 0.758 g (6.83 mmol) of calcium chloride was added. To the monatin solution, 75 ml of ethanol was added and stirred at 50 ° C. for 3 hours, then cooled to 25 ° C. over 2.5 hours, and further stirred at 25 ° C. for 10 hours. The precipitated crystals were separated by filtration and dried under reduced pressure at 40 ° C. The dried crystals were stored in a constant temperature and humidity chamber at 44 ° C. and 78% for 24 hours to obtain 4.6 g of desired calcium salt crystals.
  • Example 3 ((2R, 4R) monatin) Preparation of 2 calcium salt 4.6 hydrate 0.67 ethanol solvate crystal (2R, 4R) monatin potassium salt crystals 15g (41 mmol) in water 225ml After dissolution, 2.274 g (20.5 mmol) of calcium chloride was added. The monatin solution was heated to 50 ° C., added with 75 ml of ethanol, stirred for 1.5 hours, cooled to 25 ° C. over 2.5 hours, and further stirred at 25 ° C. for 12.5 hours. The precipitated crystals were separated by filtration and dried under reduced pressure at 40 ° C. 14.1 g of the desired calcium salt crystals were obtained.
  • Example 4 ((2R, 4R) monatin) Preparation of 2 calcium salt 5.7 hydrate crystal ((2R, 4R) monatin) 2 calcium salt crystal pentahydrate crystals 0.4 g (1.08 mmol ) was dissolved in 8.5 ml of water, heated to 65 ° C., and 8.5 ml of CH 3 CN was added. Stir at 45 ° C. for 12 hours. The precipitated crystals were separated by filtration and dried under reduced pressure at 40 ° C. to obtain 0.288 g of calcium salt crystals.
  • Example 5 ((2R, 4R) monatin) Preparation of 2 calcium salt 5.9 hydrate 0.72THF hydrate crystals (2R, 4R) monatin) 2 calcium salt crystal pentahydrate crystals 0.4 g ( 1.08 mmol) was dissolved in 8.5 ml of water, heated to 65 ° C., and 8.5 ml of THF was added. Stir at 45 ° C. for 12 hours. The precipitated crystals were separated by filtration and dried under reduced pressure at 40 ° C. to obtain 0.288 g of calcium salt crystals.
  • Example 6 ((2R, 4R) monatin) Preparation of 2 calcium salt 3.8 hydrate 0.63i-PrOH hydrate crystals ((2R, 4R) monatin) 2 calcium salt crystal pentahydrate crystals 0 0.4 g (1.08 mmol) was dissolved in 8.5 ml of water, heated to 65 ° C., and 8.5 ml of i-PrOH was added. Stir at 45 ° C. for 25 hours. The precipitated crystals were separated by filtration and dried under reduced pressure at 40 ° C. to obtain 0.337 g of calcium salt crystals.
  • Example 8 ((2R, 4R) monatin) Preparation of 2 magnesium salt dihydrate crystals (2R, 4R) Mona Tin potassium salt crystals 120 g (345 mmol) was dissolved in water 150 ml, sulfate at 60 ° C. 4.15 g (34.5 mmol) of magnesium was added. Further, 16.61 g (138 mmol) of magnesium sulfate (100 ml of water) was added over 6.4 hours. After completion of the addition, the precipitated crystals were separated by filtration and washed with 100 ml of water to obtain wet crystals (204.7 g). The wet crystals were dried under reduced pressure at 40 ° C. to obtain 105 g of magnesium salt crystals.
  • Example 9 ((2R, 4R) monatin) Preparation of 2 magnesium salt 3.1 hydrate 2.4 ethanol solvate crystal (2R, 4R) Mona tin-free substance crystals 10 g (33.3 mmol) of water After dispersing in 100 ml, 0.971 g (16.7 mmol) of magnesium hydroxide was added at 25 ° C. and stirred for 3 hours. Further, 506 ml of ethanol was added dropwise in about 3 hours, followed by stirring at 25 ° C. for 25.5 hours. The precipitated crystals (17.73 g) were filtered off and dried under reduced pressure at room temperature. 12.04 g of the desired magnesium salt crystals were obtained.
  • Example 10 ((2R, 4R) monatin) Preparation of 2 magnesium salt 7.2 hydrate 0.23 methanolate crystals (2R, 4R) Mona tin-free substance crystals 10 g (33.3 mmol) of water After dispersing in 100 ml, 0.971 g (16.7 mmol) of magnesium hydroxide was added at 25 ° C. and stirred for 3 hours. Further, 506 ml of methanol was added dropwise in about 3 hours, followed by stirring at 25 ° C. for 20 hours. The precipitated crystals (15.87 g) were filtered off and dried under reduced pressure at room temperature. 11.94 g of the desired magnesium salt crystals were obtained.
  • Example 12 ((2R, 4R) monatin) Preparation of 2 magnesium salt nonahydrate crystals (2R, 4R) Mona tin-free substance crystals 30 g (100 mmol) dispersed in water 300 ml, water at 65 ° C. 3.21 g (55 mmol) of magnesium oxide was added. Stir at 65 ° C. for 1 hour. The precipitated crystals (27.28 g) were filtered off and dried under reduced pressure at 40 ° C. for 4 hours to obtain 22.29 g of magnesium salt crystals.
  • Example 13 was obtained by the method of water vapor adsorption desorption curves a second embodiment of the crystal ((2R, 4R) monatin) obtained by the method of 2 magnesium salt tetrahydrate crystals and Example 8 (2R, 4R ) monatin) was determined water vapor adsorption desorption curves of 2 magnesium salt dihydrate crystals. The measured values are shown in FIGS.
  • Table 3 shows the results of the monatin survival rate. Calcium salt crystals and magnesium salt crystals were found to have a higher survival rate under high temperature and high humidity than potassium salt crystals.
  • Table 4 shows the results of the transmittance of the stored product solution. In the case of potassium salt crystals, the transmittance decreases and the color is yellow, but in the case of calcium salt crystals and magnesium salt crystals, no color change is observed.
  • Example 2 Storage stability evaluation (containing sucrose) Obtained in Example 1 ((2R, 4R) monatin) 2 calcium salt pentahydrate crystals, obtained in Example 2 ((2R, 4R) monatin) and 2 magnesium salt tetrahydrate crystals Preparation
  • the storage stability of the monatin monopotassium salt crystal obtained in 1 was evaluated by the following method.
  • [Storage conditions] 1 g of the sweetening composition shown in Formulation Table 2 was filled in a paper wrapping material and sealed with a heat seal. The sample was stored in a constant temperature and humidity chamber at 44 ° C. and 78% for a predetermined time, and the entire amount of the stored sample was dissolved in 50 mL of water.
  • Table 6 shows the results of the monatin survival rate. Calcium salt crystals and magnesium salt crystals were found to have a higher survival rate under high temperature and high humidity than potassium salt crystals.
  • Table 7 shows the results of the transmittance of the stored product solution. In the case of potassium salt crystals, the transmittance decreases and the color is yellow, but in the case of calcium salt crystals and magnesium salt crystals, no color change is observed.
  • [ Figure 1] is a ((2R, 4R) monatin) powder X-ray diffraction diagram after the humidity control 2 calcium salt pentahydrate crystals.
  • Example 1 [ Figure 2] is an illustration of the ((2R, 4R) monatin) optical micrograph of crystallized solution separation shortly before 2 calcium salt pentahydrate crystals. (Magnification 200 times)
  • Example 1 [Figure 3] is a ((2R, 4R) monatin) powder X-ray diffraction diagram after the humidity control 2 magnesium salt tetrahydrate crystals.
  • Figure 4] is an illustration of the ((2R, 4R) monatin) optical micrograph of crystallized solution separation shortly before 2 magnesium salt tetrahydrate crystals.
  • Example 4 is an illustration of the ((2R, 4R) monatin) optical micrograph of crystallized solution separation shortly before 2 calcium salt 5.7 hydrate crystals. (Magnification 200 times) (Example 4)
  • Figure 9 is a ((2R, 4R) monatin) powder X-ray diffraction chart after drying of 2 calcium salt 5.9 hydrate 0.72THF hydrate crystals.
  • Figure 10 is an illustration of the ((2R, 4R) monatin) optical micrograph of crystallized solution separation shortly before 2 calcium salt 5.9 hydrate 0.72THF hydrate crystals.
  • FIG. 10 is an illustration of the ((2R, 4R) monatin) optical micrograph of crystallized solution separation shortly before 2 magnesium salt 7.2 hydrate 0.23 methanolate crystals. (Magnification 200 times) (Example 10) [Figure 21] is a ((2R, 4R) monatin) powder X-ray diffraction pattern of 2 magnesium salt 8.5 hydrate 2.5DMF hydrate crystals. (Example 11) [ Figure 22] is an illustration of the (2R, 4R) monatin) optical micrograph of crystallized solution separation shortly before 2 magnesium salt 8.5 hydrate 2.5DMF hydrate crystals.

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Abstract

L'invention a pour but de proposer un nouveau cristal de monatine apte à former une composition sucrée qui résiste à une décomposition même lorsqu'elle est exposée à de la chaleur et de l'humidité conjointement avec un sel réducteur. A cet effet, selon l'invention, il a été découvert qu'un cristal de sel métallique polyvalent de (2R, 4R)-monatine résout ledit problème.
PCT/JP2012/065176 2011-06-08 2012-06-07 Cristal de sel métallique polyvalent de monatine Ceased WO2012169661A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013073679A1 (fr) * 2011-11-17 2013-05-23 味の素株式会社 Procédé de production de cristaux de sel métallique polyvalent de (2r,4r)-monatine
WO2017068034A1 (fr) * 2015-10-22 2017-04-27 Givaudan Sa Amélioration de la sucrosité
WO2017068033A1 (fr) * 2015-10-22 2017-04-27 Givaudan Sa Procédé de masquage des mauvais goûts à l'aide de cellobiose et/ou de psicose

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003045914A1 (fr) * 2001-11-30 2003-06-05 Ajinomoto Co., Inc. Cristaux de sels stereoisomeres non naturels de monatine et leur utilisation
JP2005154291A (ja) * 2003-11-21 2005-06-16 Ajinomoto Co Inc グルタミン酸誘導体の有機アミン塩及びその利用

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003045914A1 (fr) * 2001-11-30 2003-06-05 Ajinomoto Co., Inc. Cristaux de sels stereoisomeres non naturels de monatine et leur utilisation
JP2005154291A (ja) * 2003-11-21 2005-06-16 Ajinomoto Co Inc グルタミン酸誘導体の有機アミン塩及びその利用

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013073679A1 (fr) * 2011-11-17 2013-05-23 味の素株式会社 Procédé de production de cristaux de sel métallique polyvalent de (2r,4r)-monatine
WO2017068034A1 (fr) * 2015-10-22 2017-04-27 Givaudan Sa Amélioration de la sucrosité
WO2017068033A1 (fr) * 2015-10-22 2017-04-27 Givaudan Sa Procédé de masquage des mauvais goûts à l'aide de cellobiose et/ou de psicose
US11071317B2 (en) 2015-10-22 2021-07-27 Givaudan S.A. Sweetness enhancement

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