EP1154978A1 - Soluble double metal salt of group ia and iia of (-) hydroxycitric acid - Google Patents
Soluble double metal salt of group ia and iia of (-) hydroxycitric acidInfo
- Publication number
- EP1154978A1 EP1154978A1 EP99909175A EP99909175A EP1154978A1 EP 1154978 A1 EP1154978 A1 EP 1154978A1 EP 99909175 A EP99909175 A EP 99909175A EP 99909175 A EP99909175 A EP 99909175A EP 1154978 A1 EP1154978 A1 EP 1154978A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- hydroxycitric acid
- group
- iia
- salt
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- ZMJBYMUCKBYSCP-UHFFFAOYSA-N (+)-Erythro-hydroxycitric acid Natural products OC(=O)C(O)C(O)(C(O)=O)CC(O)=O ZMJBYMUCKBYSCP-UHFFFAOYSA-N 0.000 title claims abstract description 142
- ZMJBYMUCKBYSCP-AWFVSMACSA-N (1s,2r)-1,2-dihydroxypropane-1,2,3-tricarboxylic acid Chemical compound OC(=O)[C@@H](O)[C@@](O)(C(O)=O)CC(O)=O ZMJBYMUCKBYSCP-AWFVSMACSA-N 0.000 title claims abstract description 107
- 150000003839 salts Chemical class 0.000 title claims abstract description 71
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 56
- 239000002184 metal Substances 0.000 title claims abstract description 56
- 241000593508 Garcinia Species 0.000 claims abstract description 27
- 235000000885 Garcinia xanthochymus Nutrition 0.000 claims abstract description 26
- 239000000284 extract Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- 235000013361 beverage Nutrition 0.000 claims abstract description 19
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 13
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 13
- 229910001510 metal chloride Inorganic materials 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 10
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 9
- 150000002596 lactones Chemical class 0.000 claims abstract description 8
- 235000014666 liquid concentrate Nutrition 0.000 claims abstract description 6
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 3
- 230000001376 precipitating effect Effects 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 37
- 229940089491 hydroxycitric acid Drugs 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 235000008504 concentrate Nutrition 0.000 claims description 23
- 239000012141 concentrate Substances 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 241000283690 Bos taurus Species 0.000 claims description 11
- 235000013405 beer Nutrition 0.000 claims description 11
- 235000020357 syrup Nutrition 0.000 claims description 11
- 239000006188 syrup Substances 0.000 claims description 11
- 159000000007 calcium salts Chemical class 0.000 claims description 10
- 239000002798 polar solvent Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000003957 anion exchange resin Substances 0.000 claims description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 7
- 239000001110 calcium chloride Substances 0.000 claims description 7
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 4
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000003729 cation exchange resin Substances 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000001694 spray drying Methods 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- PFHZIWAVXDSFTB-UHFFFAOYSA-N hibiscusoic acid Natural products OC(=O)C1OC(=O)CC1(O)C(O)=O PFHZIWAVXDSFTB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 235000016795 Cola Nutrition 0.000 claims description 2
- 244000228088 Cola acuminata Species 0.000 claims description 2
- 235000011824 Cola pachycarpa Nutrition 0.000 claims description 2
- 229910005139 FrOH Inorganic materials 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 235000015107 ale Nutrition 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910001626 barium chloride Inorganic materials 0.000 claims description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 2
- 229910052790 beryllium Inorganic materials 0.000 claims description 2
- 229910001627 beryllium chloride Inorganic materials 0.000 claims description 2
- LWBPNIJBHRISSS-UHFFFAOYSA-L beryllium dichloride Chemical compound Cl[Be]Cl LWBPNIJBHRISSS-UHFFFAOYSA-L 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- 238000006073 displacement reaction Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910052730 francium Inorganic materials 0.000 claims description 2
- 235000012907 honey Nutrition 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 235000020004 porter Nutrition 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052705 radium Inorganic materials 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 229910001631 strontium chloride Inorganic materials 0.000 claims description 2
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 claims description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims 1
- 229910001630 radium chloride Inorganic materials 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 8
- 235000013305 food Nutrition 0.000 abstract description 6
- 159000000000 sodium salts Chemical class 0.000 description 7
- 238000003756 stirring Methods 0.000 description 5
- 235000013399 edible fruits Nutrition 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001720 carbohydrates Chemical class 0.000 description 3
- 235000014633 carbohydrates Nutrition 0.000 description 3
- 239000000796 flavoring agent Substances 0.000 description 3
- 235000019634 flavors Nutrition 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920002527 Glycogen Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 208000008589 Obesity Diseases 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
- 235000015872 dietary supplement Nutrition 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229940096919 glycogen Drugs 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000002417 nutraceutical Substances 0.000 description 2
- 235000020824 obesity Nutrition 0.000 description 2
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- RVEPHTVUPANNSH-UHFFFAOYSA-H tricalcium;1,2-dihydroxypropane-1,2,3-tricarboxylate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)C(O)C(O)(C([O-])=O)CC([O-])=O.[O-]C(=O)C(O)C(O)(C([O-])=O)CC([O-])=O RVEPHTVUPANNSH-UHFFFAOYSA-H 0.000 description 2
- 102000004146 ATP citrate synthases Human genes 0.000 description 1
- 108090000662 ATP citrate synthases Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 244000245602 Garcinia atroviridis Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VEUACKUBDLVUAC-UHFFFAOYSA-N [Na].[Ca] Chemical compound [Na].[Ca] VEUACKUBDLVUAC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 235000013351 cheese Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 235000019219 chocolate Nutrition 0.000 description 1
- 235000012000 cholesterol Nutrition 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000001079 digestive effect Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000019264 food flavour enhancer Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 241000411851 herbal medicine Species 0.000 description 1
- 235000015092 herbal tea Nutrition 0.000 description 1
- 235000008216 herbs Nutrition 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 210000000936 intestine Anatomy 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 235000020166 milkshake Nutrition 0.000 description 1
- 230000037081 physical activity Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000019553 satiation Nutrition 0.000 description 1
- 235000014102 seafood Nutrition 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000012976 tarts Nutrition 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/235—Saturated compounds containing more than one carboxyl group
- C07C59/245—Saturated compounds containing more than one carboxyl group containing hydroxy or O-metal groups
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
Definitions
- This invention relates to a new soluble double metal salt of group IA and II A of (-) hydroxycitric acid, process of preparing the same and its use in beverages and other food products without effecting their flavor and properties.
- This product with >98% purity can be used safely not only as a food supplement in various nutriceutical formulations and beverages but also for effecting obesity control.
- HCA Hydroxycitric acid
- HCA active ingredient
- Patent WO 96/36585 US patent 08/440,968 filed.
- high potassium high potassium
- the object of this invention is to overcome the above drawbacks by developing a new soluble double metal salt of (-) hydroxycitric acid which will not pose any problem in formulating with beverages and various other food products without affecting their flavor and properties.
- this invention provides a new soluble double metal salt of group IA and II A of (-) hydroxycitric acid of general fonnula I and more particularly formula II as given below:
- X is IA group metal: Li or Na or K or Rb or Cs or Fr
- Y IIA group metal: Be or Mg or Ca or Sr or Ba or Ra where concentration of X in the salt varies from 1.5 - 51.0%, the concentration of Y in the salts varies from 2.0 - 50.9%, the concentration of HCA in the salts varies from 31.0 - 93.0%) depending on the nature of X and Y. concentration of sodium in the salt : 8.58%, concentration of calcium in the salt: 14.92% concentration of (-) hydroxycitric acid : 76.50%o,
- This invention further relates to a process for preparing the said soluble metal salt of group IA and IIA of (-) hydroxycitric acid of general formula I or more particularly formula II comprising:
- Step 1 preparing (-) hydroxycitric acid liquid concentrate/solid lactone of hydroxycitric acid from Garcinia extract,
- Step 2 neutralizing the free (-) hydroxycitric acid present in the said hydroxycitric acid liquid concentrate/solid lactone present (-) hydroxycitric acid with group IA metal hydroxides
- Step 3 displacing partially group IA metal ions in the above salt solutions by adding group IIA metal chlorides to form soluble double metal salt of group IA and IIA of (-) hydroxycitric acid,
- Step 4 precipitating the said solubilised group IIA metal salts of (-) hydroxycitric acid by adding aqueous polar solvent to get soluble IIA metal salt of (-) hydroxycitric acid
- the free (-) hydroxycitric acid present in the step 2 is neutralized by three equivalents of group IA metal hydroxides.
- Partial displacement of group IA metal ion in step 3 is carried out with one equivalent of group IIA metal chloride.
- the soluble metal salt of hydroxycitric acid is obtained in powder from by spray drying prior to the solvent addition or spray drying water solubilised solvent precipitated material.
- the said polar solvents are methanol, ethanol, propanol, isopropanol and acetone.
- the (-) hydroxycitric acid concentrate in step 1 is prepared from the Garcinia extract by: i) treating the said Garcinia extract with group IA metal hydroxide to obtain soluble group LA metal salt of (-) hydroxycitric acid, ii) displacing completely the said group LA metal ions with group IIA metal ion by adding group IIA metal chlorides solution to precipitate insoluble group IIA metal salts of (-) hydroxycitric acid, iii) collecting the said precipitate of insoluble group IIA metal salt of (-) hydroxycitric acid and washing it with water, iv) adding a water soluble organic acid to the said precipitated insoluble group II A metal salt of HCA to form a stronger salt of group IIA metal and release (-) hydroxycitric acid, v) repeating the steps (iii) and (iv) to form concentrate of (-) hydroxycitric acid, vi) decolorizing the said (-) hydroxycitric acid concentrate, if desired.
- the water soluble organic acid used in step (iv) is an oxalic acid.
- the (-) hydroxycitric acid concentrate in step 1 is also prepared from the Garcinia by: i) extracting Garcinia rind with aqueous polar solvent and filtering, ii) heating the filtrate in vacuum at 50-80° C to evaporate the said polar solvent, iii) removing the water insoluble substances to get the (-) hydroxycitric acid concentrate, iv) decolorizing the said (-) hydroxycitric acid concentrate, if necessary.
- the aqueous polar solvent used in step 1 is 80% acetone in water.
- the (-) hydroxycitric acid concentrate in step 1 is also prepared from the
- Garcinia extract by: i) loading the Garcinia extract containing free (-) hydroxycitric acid on anion exchange resin column, ii) washing the said column with group IA metal hydroxide solution to get group IA metal salt of (-) hydroxycitric acid, iii) loading the said group LA metal salt solution of (-) hydroxycitric acid on cation exchange resin to get free (-) hydroxycitric acid, iv) heating the said free (-) hydroxycitric acid in vacuum to evaporate water and get the (-) hydroxycitric acid concentrate. v) decolorizing the said (-) hydroxycitric acid concentrate, if necessary.
- the said (-) hydroxycitric acid concentrate is decolorized by heating with 2- 5% activated charcoal, if desired.
- the said lactone of (-) hydroxycitric acid in step 1 is prepared by: i) heating the (-) hydroxycitric acid concentrate at 67° C to form syrup of (-) hydroxycitric acid lactone, ii) drying and desiccating the said syrup to get solid mass of (-) hydroxycitric acid lactone.
- a process for the preparation of soluble double metal salt of group IA and IIA of (-) hydroxycitric acid comprising: i) loading Garcinia extract containing free (-) hydroxycitric acid on an anion exchange resin column, ii) washing the said anion exchange resin column with Group IA metal hydroxide to obtain group IA metal salt of (-) hydroxycitric acid solution. iii) treating the said group IA metal salt of (-) hydroxycitric acid partially with group IIA metal chloride to get soluble double metal salt of group IA and IIA of (-) hydroxycitric acid.
- Group IA metal hydroxides used are LiOH, NaOH, KOH, RbOH, CsOH and FrOH.
- Group IIA metal chlorides BeCl 2 , MgCI 2 , CaCI 2 , SrCl 2 , BaCl 2 and RaC12.
- the soluble double metal salt of group IA and IIA of (-) hydroxycitric acid is soluble sodium calcium salt of (-) hydroxycitric acid.
- Example 1 The process will now be described with reference to the following examples.
- Example 1 Example 1 :
- Water extract of Garcinia rind is obtained by counter current extraction, this is carried out in three vessels more specifically each time fresh Garcinia rind each time lKg is loaded into vessel 3 and treated with 1.5 liters of water, the rind is moved from V 3 to V 2 then to Vj. On the other hand the extract was moved from V ! to V 2 then to V 3 .
- the extract obtained starting from 3Kgs of rind was 3.6 litres containing 620gms of acid along with the other water-soluble substances.
- the total soluble constituents in the extract i.e. brix was found to be 43 degrees.
- the extraction efficiency was found to be 90%.
- This acid was transferred to a vessel and neutralized by addition if 358 gm of sodium hydroxide. After cooling this solution to room temperature, 500 ml of solution containing 490 gm of calcium chloride was added to it and resultant insoluble calcium salt was centrifuged and washed thoroughly to removed the color and water soluble impurities.
- the salt obtained was dried and weight is found to be 693 gm.
- the solution of hydroxycitric acid thus obtained was found to contain 202 gm of acid in 450 ml of extract. This was neutralized by 117 gm of sodium hydroxide and the solution was cooled to room temperature. To this sodium salt solution of hydroxycitric acid, 200 ml of solution containing 81 gm of calcium chloride was added drop wise with vigorous stirring. The soluble calcium salt of hydroxycitric acid was then precipitated by addition of ethanol. Then precipitated salt was filtered, washed with ethanol and dried to obtain 234 gm of the soluble calcium salt of hydroxycitric acid (yield: 91.2%).
- An anion exchange resin (bed volume IL) was loaded onto a glass column and washed thoroughly with 10% aqueous sodium hydroxide to remove the chloride present in the resin. The column was then washed with water till the eluate pH was neutral. Three hundred milliliters of an aqueous solution containing 108 gm of (-) hydroxycitric acid was loaded onto the column and washed with water to remove the colored materials. The column was eiuted with 1 liter of an aqueous solution containing 63 gm of sodium hydroxide followed by 0.5 L of water. The combined eluate (1.5 liters) containing sodium salt of hydroxycitric acid was divided into two parts (750 ml each) and the soluble calcium salt was prepared as follows.
- a portion of the sodium salt of hydroxycitric acid (750 ml) was concentrated to 200 ml. Fifty milliliters of a solution containing 20.25 gm of calcium chloride was added drop wise with vigorous stirring. The soluble salt of hydroxycitric acid thus formed was precipitated by the addition of ethanol, collected by filtration, washed with ethanol and dried to obtain 60.3 gm of the soluble calcium salt of hydroxycitric acid (yield: 91.8%). b) The remaining portion of the eluate (750-ml) from the anion exchange column was passed through a column of cation exchange resin (bed volume 750 ml). The column was washed with water until the pH of the eluent reached neutral.
- This invention also provides the use of the said soluble double metal salt of group IA and IIA of (-) hydroxycitric acid of formula I and particularly formula II in beverages and other food products.
- the said beverage is a Pilsner, beer containing alcohol content 3.0-3.8 weight % or Dortmund beer containing alcohol content 2.5-4.0 weight % or Kunststoff beer containing alcohol content 2.0-5.0 weight % or Kunststoff Ale or Porter beer containing alcohol contents 2.0-5.0 weight % or Stout beer containing alcohol content 5.0-6.5 weight %, each said beer includes the soluble double metal salt of group IA or IIA of formula I or II in the proportion 0.01-0.5 % w/v.
- the said beverage is aerated or non-aerated beverage/colas and the syrups are either processed or naturally occurring like honey including soluble double metal salt of group IA and IIA of (-) hydroxycitric acid of formula I or II in the proportion 0.01-10 % w/v.
- Soluble double metal salt of group IA and IIA of (-) hydroxycitric acid of formula I or formula II in the proportion 0.01-10 % w/v is added at any stage during the production of the beverage or processed syrups.
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Abstract
This invention relates to a new soluble double salt of group IA and group IIA of (-)hydroxycitric acid of general formulas (I) and particularly (II). This invention also includes a process of preparing the soluble double metal salt of groups IA and IIA of (-)hyroxycitric acid of general formula (I) comprising preparing (-)hyroxycitric acid liquid concentrate/solid lactone thereof from Garcinia extract, neutralizing the free (-)hydroxycitric acid present in the said (-)hydroxycitric acid liquid concentrate/solid lactone (-)hydroxycitric acid with group IA metal hydroxides, displacing partially the group IA metal ions in the above salt solutions by adding group IIA metal chlorides to form soluble double metal salt of group IA and IIA of (-)hydroxycitric acid, and precipitating the said double metal salt. The instant invention also disclosed the use of the said soluble double metal salt of (-)hyroxycitric acid in beverages and other food products.
Description
Soluble double metal salt of group IA and IIA of (-) hydroxycitric acid Technical field
This invention relates to a new soluble double metal salt of group IA and II A of (-) hydroxycitric acid, process of preparing the same and its use in beverages and other food products without effecting their flavor and properties. This product with >98% purity can be used safely not only as a food supplement in various nutriceutical formulations and beverages but also for effecting obesity control. Background Art
(-) Hydroxycitric acid (HCA) occurs in the fruit rind of Garcinia species (G. Cambogia, G indica and G. atroviridis). The first two species grow abundantly in India and the third occurs mostly in South East Asian countries. The success of this natural food product derived from Garcinia fruit has been documented and been in use since several centuries BC. Also known as "Kokum", the extracts of the fruit have been used as a tart flavoring in meat and seafood dishes, turned into a refreshing beverage that serves as a unique flavor enhancer, gourmet spice and a digestive after a heavy meal. In Ayurveda, the traditional ancient system of herbal medicine in India, Garcinia is also considered to be one of the prime herbs that are beneficial for the heart.
In more recent times, Garcinia has received worldwide attention as a nutriceutical for effective obesity control. Several scientists including at Hoffman- La Roche have established that HCA, the active ingredient in the fruit, prevents the conversion of excess carbohydrates to fat in animals. The energy released by the excess carbohydrate is converted into and stored as glycogen, a readily usable form of energy. Interestingly, it has been shown to inhibit ATP dependent citrate-lyase, a key enzyme in diverting carbohydrate to fatty acids and cholesterol synthesis. (Sullivan et al. Lipids, 9:121 and 129 (1973), Sergio, W., Medical Hypothesis 27:39 (1988).
The age-old practice of consuming Garcinia rind as a food additive by inhabitants of Malabar and Konkan coast of the Indian peninsula has established
the safety of HCA. The isolation and chemical nature of (-) hydroxycitric acid from Garcinia rind are described in the publication of Lewis Y.S., et al. (Methods in Enzymology, 13:613 (1967) and in the patents (Indian patents 160753 & 178298 and US patents 5536516 & 5656314). It is believed that consumption of HCA influences the body metabolism leading to the saturation of glycogen receptors in the liver and a consequent transmission of signals of satiation to brain. Even as a food supplement, (-) HCA helps a person to lose/control weight in a natural way without affecting normal physical activities. In view of its unique property, several health care formulations incorporating HCA are being sold across the counter in the Western markets. These include tablets, capsules, herbal teas, chocolate bars, milk shakes and other beverages. The active ingredient (HCA) from this insoluble HCA salt is released upon contact with hydrochloric acid in the stomach and absorbed through the intestine to exert its metabolic effect.
There is prior art on the preparation of a soluble tri-potassium salt of (-)
HCA (Lewis Y.S., et al (Methods in Enzymology, 13:613 (1967), International
Patent WO 96/36585, US patent 08/440,968 filed). However, its alkaline nature and risks associated with the consumption of high potassium (-36%) makes this product unsuitable for HCA-based formulations.
In our earlier patents (Indian patent No. 178298 & US patents 5536516, 5656314) which describes preparation of a concentrate of (-) hydroxycitric acid and its lactone in liquid form, comprising of several steps like water extraction of Garcinia rind containing (-) hydroxycitric acid and its concentration, acetone refinement of this concentrated water extract, evaporation of acetone, loading thus obtained refined extract on ion-exchange columns containing an anion exchange resin followed by a cation exchange resin, and finally evaporation of the free acid liberated from the ion-exchange process to said concentration. This liquid form of (-) hydroxycitric acid has problems of stability and half-life.
Disclosure of the Invention
In addition, its highly acidic nature poses problems in formulating into beverage and various other food products without affecting their flavor and properties. The object of this invention is to overcome the above drawbacks by developing a new soluble double metal salt of (-) hydroxycitric acid which will not pose any problem in formulating with beverages and various other food products without affecting their flavor and properties.
To achieve the said objective, this invention provides a new soluble double metal salt of group IA and II A of (-) hydroxycitric acid of general fonnula I and more particularly formula II as given below:
Formula I Formula II
Where X is IA group metal: Li or Na or K or Rb or Cs or Fr
Where Y is IIA group metal: Be or Mg or Ca or Sr or Ba or Ra where concentration of X in the salt varies from 1.5 - 51.0%, the concentration of Y in the salts varies from 2.0 - 50.9%, the concentration of HCA in the salts varies from 31.0 - 93.0%) depending on the nature of X and Y. concentration of sodium in the salt : 8.58%, concentration of calcium in the salt: 14.92% concentration of (-) hydroxycitric acid : 76.50%o,
This invention further relates to a process for preparing the said soluble metal salt of group IA and IIA of (-) hydroxycitric acid of general formula I or more particularly formula II comprising:
Step 1 : preparing (-) hydroxycitric acid liquid concentrate/solid lactone of hydroxycitric acid from Garcinia extract,
Step 2: neutralizing the free (-) hydroxycitric acid present in the said hydroxycitric acid liquid concentrate/solid lactone present (-) hydroxycitric acid with group IA metal hydroxides
Step 3: displacing partially group IA metal ions in the above salt solutions by adding group IIA metal chlorides to form soluble double metal salt of group IA and IIA of (-) hydroxycitric acid,
Step 4: precipitating the said solubilised group IIA metal salts of (-) hydroxycitric acid by adding aqueous polar solvent to get soluble IIA metal salt of (-) hydroxycitric acid The free (-) hydroxycitric acid present in the step 2 is neutralized by three equivalents of group IA metal hydroxides.
Partial displacement of group IA metal ion in step 3 is carried out with one equivalent of group IIA metal chloride.
The soluble metal salt of hydroxycitric acid is obtained in powder from by spray drying prior to the solvent addition or spray drying water solubilised solvent precipitated material.
The said polar solvents are methanol, ethanol, propanol, isopropanol and acetone.
The (-) hydroxycitric acid concentrate in step 1 is prepared from the Garcinia extract by: i) treating the said Garcinia extract with group IA metal hydroxide to obtain soluble group LA metal salt of (-) hydroxycitric acid,
ii) displacing completely the said group LA metal ions with group IIA metal ion by adding group IIA metal chlorides solution to precipitate insoluble group IIA metal salts of (-) hydroxycitric acid, iii) collecting the said precipitate of insoluble group IIA metal salt of (-) hydroxycitric acid and washing it with water, iv) adding a water soluble organic acid to the said precipitated insoluble group II A metal salt of HCA to form a stronger salt of group IIA metal and release (-) hydroxycitric acid, v) repeating the steps (iii) and (iv) to form concentrate of (-) hydroxycitric acid, vi) decolorizing the said (-) hydroxycitric acid concentrate, if desired. The water soluble organic acid used in step (iv) is an oxalic acid. The (-) hydroxycitric acid concentrate in step 1 is also prepared from the Garcinia by: i) extracting Garcinia rind with aqueous polar solvent and filtering, ii) heating the filtrate in vacuum at 50-80° C to evaporate the said polar solvent, iii) removing the water insoluble substances to get the (-) hydroxycitric acid concentrate, iv) decolorizing the said (-) hydroxycitric acid concentrate, if necessary. The aqueous polar solvent used in step 1 is 80% acetone in water. The (-) hydroxycitric acid concentrate in step 1 is also prepared from the
Garcinia extract by: i) loading the Garcinia extract containing free (-) hydroxycitric acid on anion exchange resin column, ii) washing the said column with group IA metal hydroxide solution to get group IA metal salt of (-) hydroxycitric acid, iii) loading the said group LA metal salt solution of (-) hydroxycitric acid on cation exchange resin to get free (-) hydroxycitric acid, iv) heating the said free (-) hydroxycitric acid in vacuum to evaporate water and get the (-) hydroxycitric acid concentrate.
v) decolorizing the said (-) hydroxycitric acid concentrate, if necessary.
The said (-) hydroxycitric acid concentrate is decolorized by heating with 2- 5% activated charcoal, if desired.
The said lactone of (-) hydroxycitric acid in step 1 is prepared by: i) heating the (-) hydroxycitric acid concentrate at 67° C to form syrup of (-) hydroxycitric acid lactone, ii) drying and desiccating the said syrup to get solid mass of (-) hydroxycitric acid lactone.
A process for the preparation of soluble double metal salt of group IA and IIA of (-) hydroxycitric acid comprising: i) loading Garcinia extract containing free (-) hydroxycitric acid on an anion exchange resin column, ii) washing the said anion exchange resin column with Group IA metal hydroxide to obtain group IA metal salt of (-) hydroxycitric acid solution. iii) treating the said group IA metal salt of (-) hydroxycitric acid partially with group IIA metal chloride to get soluble double metal salt of group IA and IIA of (-) hydroxycitric acid.
Group IA metal hydroxides used are LiOH, NaOH, KOH, RbOH, CsOH and FrOH. Group IIA metal chlorides BeCl2, MgCI2, CaCI2, SrCl2, BaCl2 and RaC12.
The soluble double metal salt of group IA and IIA of (-) hydroxycitric acid is soluble sodium calcium salt of (-) hydroxycitric acid.
The process will now be described with reference to the following examples. Example 1 :
Water extract of Garcinia rind is obtained by counter current extraction, this is carried out in three vessels more specifically each time fresh Garcinia rind each time lKg is loaded into vessel 3 and treated with 1.5 liters of water, the rind is
moved from V3 to V2 then to Vj. On the other hand the extract was moved from V! to V2 then to V3.
The extract obtained starting from 3Kgs of rind was 3.6 litres containing 620gms of acid along with the other water-soluble substances. The total soluble constituents in the extract i.e. brix was found to be 43 degrees. The extraction efficiency was found to be 90%. This acid was transferred to a vessel and neutralized by addition if 358 gm of sodium hydroxide. After cooling this solution to room temperature, 500 ml of solution containing 490 gm of calcium chloride was added to it and resultant insoluble calcium salt was centrifuged and washed thoroughly to removed the color and water soluble impurities. The salt obtained was dried and weight is found to be 693 gm.
One hundred grams of this insoluble salt was taken in a one liter vessel to and 71.32 gm oxalic acid dihydrate dissolved in 350 ml of water was added and stirred at 150 RPM on a shaker for 30 min, and the supernatant 210 ml of was collected. To this supernatant 71.32 gm of oxalic acid dihydrate was added and another 100 gm of calcium hydroxycitrate added and this procedure is followed until the hydroxycitric acid content in the extract reaches -45% detected by high performance liquid chromatography (HPLC). The traces of oxalic acid were also removed by finally adding excess calcium hydroxycitrate. This was monitored by HPLC by observing the total absence of oxalic acid peak. The solution of hydroxycitric acid thus obtained was found to contain 202 gm of acid in 450 ml of extract. This was neutralized by 117 gm of sodium hydroxide and the solution was cooled to room temperature. To this sodium salt solution of hydroxycitric acid, 200 ml of solution containing 81 gm of calcium chloride was added drop wise with vigorous stirring. The soluble calcium salt of hydroxycitric acid was then precipitated by addition of ethanol. Then precipitated salt was filtered, washed with ethanol and dried to obtain 234 gm of the soluble calcium salt of hydroxycitric acid (yield: 91.2%). In another experiment, the above procedure was repeated exactly after collecting the ethanol precipitated material. This was again dissolved in water
to 30% and the material thus obtained was spray dried to obtain 243 gm of the soluble salt of hydroxycitric acid (yield 95%). EXAMPLE 2:
One hundred gm Garcinia Cambogia rind was extracted 4 times with 80% acetone in water (250 ml each time) for 4 hours. The combined extract (830-ml) was concentrated to 300 ml by heating m vacuo at 56°C (500 millibar and filtered through cheese cloth to remove water insoluble non polar substances. The filtrate (260-ml) containing 18 gm of hydroxycitric acid decolorized by addition of 2.6 gm of activated charcoal and filtered. The resultant clear solution was concentrated to 50 ml, and the free acid was converted into the sodium salt of hydroxycitric acid by the addition of 1 1 gm of sodium hydroxide pellets, were added. To this formed solution of sodium salt of (-) hydroxycitric acid 20 ml of solution containing 9 gm of calcium chloride was added drop wise with vigorous stirring. The soluble salt of hydroxycitric acid is then precipitated by addition of ethanol. The precipitated salt is filtered, washed with ethanol and dried to obtain 20.7 gm of the soluble calcium salt of hydroxycitric acid (yield 89.84%). EXAMPLE 3:
An anion exchange resin (bed volume IL) was loaded onto a glass column and washed thoroughly with 10% aqueous sodium hydroxide to remove the chloride present in the resin. The column was then washed with water till the eluate pH was neutral. Three hundred milliliters of an aqueous solution containing 108 gm of (-) hydroxycitric acid was loaded onto the column and washed with water to remove the colored materials. The column was eiuted with 1 liter of an aqueous solution containing 63 gm of sodium hydroxide followed by 0.5 L of water. The combined eluate (1.5 liters) containing sodium salt of hydroxycitric acid was divided into two parts (750 ml each) and the soluble calcium salt was prepared as follows.
A portion of the sodium salt of hydroxycitric acid (750 ml) was concentrated to 200 ml. Fifty milliliters of a solution containing 20.25 gm of calcium chloride was
added drop wise with vigorous stirring. The soluble salt of hydroxycitric acid thus formed was precipitated by the addition of ethanol, collected by filtration, washed with ethanol and dried to obtain 60.3 gm of the soluble calcium salt of hydroxycitric acid (yield: 91.8%). b) The remaining portion of the eluate (750-ml) from the anion exchange column was passed through a column of cation exchange resin (bed volume 750 ml). The column was washed with water until the pH of the eluent reached neutral. One liter of the flow through which contained 45 gm of free (-) hydroxycitric acid was collected, concentrated in Vacuo to 100 ml and reneutralized by the addition of 27 gm of sodium hydroxide pellets. To the resultant solution of the sodium salt of (-) hydroxycitric acid, 50 ml of a solution containing 18 gm of calcium chloride was added drop wise with vigorous stirring. The resultant soluble calcium salt of hydroxycitric acid was precipitated by the addition of ethanol. The precipitated salt was filtered, washed with ethanol and dried to obtain 54 gm of the soluble calcium salt of (-) hydroxycitric acid (yield:
93.75%). EXAMPLE 4:
One hundred milliliters of 48% enriched aqueous solution of (-) hydroxycitric acid solution was evaporated 670 C in vacuo to remove water. The syrup thus formed was transferred into petridishes dried and desiccated under vacuum for 4-5 hours. The solid lactone of hydroxycitric acid weighing 30.6 gm was collected. To the said lactone residue, 60 ml of a solution containing 18 gm of sodium hydroxide was added. To the resultant solution of the sodium salt of (-) hydroxycitric acid, 30 ml of a solution containing 12.6 gm of calcium chloride was added drop wise with vigorous stirring. The soluble salt of hydroxycitric acid is then precipitated by addition of ethanol. The precipitated salt was filtered, washed with ethanol and dried to obtain 36 gm of the soluble calcium salt of hydroxycitric acid (yield: 91.91%).
This invention also provides the use of the said soluble double metal salt of group IA and IIA of (-) hydroxycitric acid of formula I and particularly formula II in beverages and other food products.
Beverages containing 0-15 weight % alcohol and syrups including soluble double metal salt of group IA and IIA of (-) hydroxycitric acid of formula I or formula II in the proportion 0.01 -10 % w/v.
The said beverage is a Pilsner, beer containing alcohol content 3.0-3.8 weight % or Dortmund beer containing alcohol content 2.5-4.0 weight % or Munich beer containing alcohol content 2.0-5.0 weight % or Munich Ale or Porter beer containing alcohol contents 2.0-5.0 weight % or Stout beer containing alcohol content 5.0-6.5 weight %, each said beer includes the soluble double metal salt of group IA or IIA of formula I or II in the proportion 0.01-0.5 % w/v.
The said beverage is aerated or non-aerated beverage/colas and the syrups are either processed or naturally occurring like honey including soluble double metal salt of group IA and IIA of (-) hydroxycitric acid of formula I or II in the proportion 0.01-10 % w/v.
Soluble double metal salt of group IA and IIA of (-) hydroxycitric acid of formula I or formula II in the proportion 0.01-10 % w/v is added at any stage during the production of the beverage or processed syrups.
Claims
1. A new soluble double metal salt of group IA and IIA of (-) hydroxycitric acid of general formula I as given below:
10 Formula II where X is IA group metal : Li or Na or K or Rb or Cs or Fr Where Y is IIA group metal: Be or Mg or Ca or Sr or Ba or Ra where the concentration of X in the salt varies from 1.5 - 51.0%, the concentration of Y in the salts varies from 2.0 - 50.9% the concentration of HCA in the salt varies from 31.0 -93.0% depending on the nature of X and Y.
2. A new soluble double metal salt of group I A and IIA of (-) hydroxycitric acid as claimed in claim 1, characterized by X is Na+ and Y is Ca ^.
Concentration of sodium in the salt: 8.58% Concentration of calcium in the salt: 14.92%) Concentration of (-) hydroxycitric acid: 76.50%>,
3. A process of preparing the soluble double metal salt of group IA and IIA of (-) hydroxycitric acid of general formula I as claimed in claim 1 characterized by:
Preparing (-) hydroxycitric acid liquid concentrate/ solid lactone of hydroxycitric acid from Garcinia extract, neutralizing the free (-) hydroxycitric acid present in the said (-) hydroxycitric acid liquid concentrate/solid lactone (-) hydroxycitric acid with group IA metal hydroxides, displacing partially the group IA metal ions in the above salt solutions by adding group IIA metal chlorides to form soluble double metal salt of group IA and IIA of (-) hydroxycitric acid, precipitating the said solubilised group IIA metal salts of (-) hydroxycitric acid by adding aqueous polar solvent to get soluble IIA metal salt of (-) hydroxycitric acid 4. A process as claimed in claim 3 characterized by soluble metal salt of hydroxy citric acid is obtained in powder from by spray drying prior to the solvent addition or spray drying water solubilised solvent precipitated material.
5. A process as claimed in claim 3 characterized by the preparation of (-) hydroxycitric acid concentrate from the Garcinia extract comprising: treating the said Garcinia extract with group IA metal hydroxide to obtain soluble group LA metal salt of (-) hydroxycitric acid, displacing completely the said group IA metal ions with group IIA metal ion by adding group IIA metal chlorides solution to precipitate insoluble group IIA metal salts of (-) hydroxycitric acid, collecting the said precipitate of insoluble group IIA metal salt of (-) hydroxycitric acid and washing it with water, adding a water soluble organic acid to the said precipitated insoluble group IIA metal salt of HCA to form a stronger salt of group IIA metal and release (-) hydroxycitric acid, repeating the steps (iii) and (iv) to form concentrate of (-) hydroxycitric acid, decolorizing the said (-) hydroxycitric acid concentrate, if desired.
6. A process as claimed in claim 3 characterized by the preparation of hydroxycitric acid concentrate from the Garcinia extract comprising: extracting Garcinia rind with aqueous polar solvent and filtering, heating the filtrate in vacuum at 50-80°C to evaporate the said polar solvent, removing the water insoluble substances to get the (-) hydroxycitric acid concentrate. decolorizing the said (-) hydroxycitric acid concentrate, if necessary.
7. A process as claimed in claim 3 characterized by the preparation of (-) hydroxycitric acid concentrate from the Garcinia extract comprising: loading the Garcinia extract containing free (-) hydroxycitric acid on anion exchange resin column, washing the said column with group IA metal hydroxide solution to get group IA metal salt of (-) hydroxycitric acid, - loading the said group IA metal salt solution of (-) hydroxycitric acid on cation exchange resin to get free (-) hydroxycitric acid, heating the said free (-) hydroxycitric acid in vacuum to evaporate water and get the (-) hydroxycitric acid concentrate decolorizing the said (-) hydroxycitric acid concentrate, if necessary.
8. A process as claimed in claim 3 characterized by: loading the Garcinia extract containing free (-) hydroxycitric acid on anion exchange resin column, washing the said anion exchange resin column with group IA metal hydroxide to obtain group IA metal salt of (-) hydroxycitric acid solution, - treating the said group LA metal salt of (-) hydroxycitric acid partially with group IIA metal chloride to get soluble group IIA metal salt of (-) hydroxycitric acid.
9. A process as claimed in claim 3 characterized by the solid lactone of (-) hydroxycitric acid is prepared by: - heating the (-) hydroxycitric acid concentrate at 67°C to form syrup of
(-) hydroxycitric acid lactone drying and desiccating the said syrup to get solid mass of (-) hydroxycitric acid lactone.
10. A process as claimed in claim 3 characterized by the free (-) hydroxycitric acid present in step 2 is neutralized by three equivalents of group IA metal hydroxides.
11. A process as claimed in claim 5 characterized by the said water soluble organic acid is an oxalic acid.
12. A process as claimed in claim 1 characterized by the said (-) hydroxycitric acid concentrate is decolorized by heating with 2-5 % activated charcoal, if desired.
13. A process as claimed in claim 3 characterized by partial displacement of group IA metal ion in step 3 is carried out with one equivalent of group IIA metal chloride.
14. A process as claimed in claim 3 characterized by group LA metal hydroxides used are LiOH, NaOH, , RbOH, CsOH and FrOH and group IIA metal chlorides used are BeCl2, MgCl2, CaCl2, SrCl2, BaCl2 and RaCl2.
15. A process as claimed in claim 3 characterized by the said polar solvents are methanol, ethanol, propanol, isopropanol and acetone.
16. A process as claimed in claim 3 characterized by the aqueous polar solvent is 80%) acetone in water.
17. A process as claimed in claim 1 of the preceding claims characterized by soluble group IIA metal salt of (-) hydroxycitric acid is soluble calcium salt of (-) hydroxycitric acid.
18. Beverages containing 0-15 weight % alcohol and syrups including soluble double metal salt of group IA and IIA of (-) hydroxycitric acid of formula I or formula II in the proportion 0.01-10 %> w/v.
19. Beverages as claimed in claim 18 characterized by the said beverage is a Pilsner beer containing alcohol contents 3.0 -3.8 weight % or Dortmund beer containing alcohol contents 2.5 - 4.0 weight % or Munich beer containing alcohol contents 2.5 - 5.0 weight % or Munich Ale or Porter beer containing alcohol content 5.0 - 6.5 weight %, each said beer includes the soluble double metal salt of group IA or IIA of formula I or II in the proportion 0.01 - 0.5 % w/v.
20. Beverages and syrups as claimed in claim 18 characterized by the said beverage is aerated or non-aerated beverage/colas and the syrups are either processed or naturally occurring like honey including soluble double metal salt of group IA or IIA of (-) hydroxycitric acid of formula I or II in the proportion 0.01- 10 % w/v.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/IN1999/000004 WO2000048983A1 (en) | 1999-02-18 | 1999-02-18 | Soluble double metal salt of group ia and iia of (-) hydroxycitric acid |
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| Publication Number | Publication Date |
|---|---|
| EP1154978A1 true EP1154978A1 (en) | 2001-11-21 |
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|---|---|---|---|
| EP99909175A Withdrawn EP1154978A1 (en) | 1999-02-18 | 1999-02-18 | Soluble double metal salt of group ia and iia of (-) hydroxycitric acid |
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| EP (1) | EP1154978A1 (en) |
| JP (1) | JP2002542152A (en) |
| AU (1) | AU2851799A (en) |
| CA (1) | CA2364245C (en) |
| IL (1) | IL144827A0 (en) |
| WO (1) | WO2000048983A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1011660A1 (en) | 1997-07-14 | 2000-06-28 | Inter-Health Nutraceuticals Incorporated | Hydroxycitric acid compositions, pharmaceutical and dietary supplements and food products made therefrom, and methods for their use in reducing body weight |
| US7119110B2 (en) | 2001-10-05 | 2006-10-10 | Interhealth Nutraceuticals Incorporated | Method and composition for preventing or reducing the symptoms of insulin resistance syndrome |
| US20030119913A1 (en) | 2001-12-20 | 2003-06-26 | Ohia Sunny E. | Method for increasing serotonin levels in a person by administration of a composition incorporating (-)-hydroxycitric acid, and related compositions thereof |
| US6875891B2 (en) * | 2003-05-12 | 2005-04-05 | Laila Impex | Process for preparing highly water soluble double salts of hydroxycitric acid particularly alkali and alkaline earth metal double salts |
| EP1713454A4 (en) * | 2003-09-11 | 2008-07-02 | Glykon Technologies Group Llc | Enteric delivery of (-)-hydroxycitric acid |
| EP2125691A4 (en) * | 2007-02-16 | 2012-02-01 | Vittal Mallya Scient Res Foundation | (-) HYDROXYCITRIC ACID METAL SALT DERIVATIVES OF HIGH PURITY AND METHOD FOR THE PREPARATION THEREOF |
| JP2011079752A (en) * | 2009-10-05 | 2011-04-21 | Kracie Home Products Ltd | Pancreatic lipase inhibitor, food and beverage composition containing the same and pharmaceutical composition |
| CN110087646A (en) * | 2016-09-08 | 2019-08-02 | 格利康科技集团有限责任公司 | Monomeric bimetallic hydroxycitric acid compound and methods for its preparation and use |
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|---|---|---|---|---|
| US3536630A (en) * | 1968-05-21 | 1970-10-27 | Us Agriculture | Calcium sequestration in highly alkaline medium |
| US5536516A (en) * | 1994-08-24 | 1996-07-16 | Renaissance Herbs, Inc. | Hydroxycitric acid concentrate and food products prepared therefrom |
| AU5736096A (en) * | 1995-05-15 | 1996-11-29 | Sabinsa Corporation | A new process for the production of potassium hydroxy citric acid, and compositions containing the potassium hydroxy cit ric acid |
-
1999
- 1999-02-18 WO PCT/IN1999/000004 patent/WO2000048983A1/en not_active Ceased
- 1999-02-18 CA CA2364245A patent/CA2364245C/en not_active Expired - Fee Related
- 1999-02-18 EP EP99909175A patent/EP1154978A1/en not_active Withdrawn
- 1999-02-18 JP JP2000599724A patent/JP2002542152A/en not_active Withdrawn
- 1999-02-18 IL IL14482799A patent/IL144827A0/en unknown
- 1999-02-18 AU AU28517/99A patent/AU2851799A/en not_active Abandoned
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| CA2364245C (en) | 2010-10-05 |
| WO2000048983A1 (en) | 2000-08-24 |
| AU2851799A (en) | 2000-09-04 |
| CA2364245A1 (en) | 2000-08-24 |
| JP2002542152A (en) | 2002-12-10 |
| IL144827A0 (en) | 2002-06-30 |
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