US20020177584A1 - Single pot process for preparing metal picolinates from alpha pecoline - Google Patents
Single pot process for preparing metal picolinates from alpha pecoline Download PDFInfo
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- US20020177584A1 US20020177584A1 US09/983,897 US98389701A US2002177584A1 US 20020177584 A1 US20020177584 A1 US 20020177584A1 US 98389701 A US98389701 A US 98389701A US 2002177584 A1 US2002177584 A1 US 2002177584A1
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- United States
- Prior art keywords
- chromium
- alpha
- zinc
- metal
- picolinate
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- 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.)
- Granted
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 48
- 239000002184 metal Substances 0.000 title claims abstract description 48
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical class OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title description 5
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 40
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- FZGNXCUHCKHKQX-UHFFFAOYSA-N pyridine-2-carboxylic acid;sulfuric acid Chemical compound OS(O)(=O)=O.OC(=O)C1=CC=CC=N1 FZGNXCUHCKHKQX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 235000011149 sulphuric acid Nutrition 0.000 claims abstract description 11
- 239000001117 sulphuric acid Substances 0.000 claims abstract description 11
- SIOXPEMLGUPBBT-UHFFFAOYSA-M picolinate Chemical compound [O-]C(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-M 0.000 claims abstract description 10
- 235000015872 dietary supplement Nutrition 0.000 claims abstract description 6
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000011541 reaction mixture Substances 0.000 claims abstract description 5
- 239000007800 oxidant agent Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 229940046374 chromium picolinate Drugs 0.000 claims description 9
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 9
- GJYSUGXFENSLOO-UHFFFAOYSA-N chromium;pyridine-2-carboxylic acid Chemical compound [Cr].OC(=O)C1=CC=CC=N1.OC(=O)C1=CC=CC=N1.OC(=O)C1=CC=CC=N1 GJYSUGXFENSLOO-UHFFFAOYSA-N 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- NHVUUBRKFZWXRN-UHFFFAOYSA-L zinc;pyridine-2-carboxylate Chemical class C=1C=CC=NC=1C(=O)O[Zn]OC(=O)C1=CC=CC=N1 NHVUUBRKFZWXRN-UHFFFAOYSA-L 0.000 claims description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- 239000011651 chromium Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229940032991 zinc picolinate Drugs 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 6
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 6
- 239000011686 zinc sulphate Substances 0.000 claims description 6
- 235000009529 zinc sulphate Nutrition 0.000 claims description 6
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 5
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- NMWDYLYNWRFEMR-UHFFFAOYSA-N 2-methylpyridine Chemical group CC1=CC=CC=N1.CC1=CC=CC=N1 NMWDYLYNWRFEMR-UHFFFAOYSA-N 0.000 claims description 3
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- XHFVDZNDZCNTLT-UHFFFAOYSA-H chromium(3+);tricarbonate Chemical compound [Cr+3].[Cr+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O XHFVDZNDZCNTLT-UHFFFAOYSA-H 0.000 claims description 3
- QOWZHEWZFLTYQP-UHFFFAOYSA-K chromium(3+);triformate Chemical compound [Cr+3].[O-]C=O.[O-]C=O.[O-]C=O QOWZHEWZFLTYQP-UHFFFAOYSA-K 0.000 claims description 3
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 3
- 239000003517 fume Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 235000013904 zinc acetate Nutrition 0.000 claims description 3
- 235000004416 zinc carbonate Nutrition 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- -1 chromium picolinates Chemical class 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000009423 ventilation Methods 0.000 claims description 2
- 239000011667 zinc carbonate Substances 0.000 claims description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 2
- 238000007796 conventional method Methods 0.000 claims 1
- 229940081066 picolinic acid Drugs 0.000 description 10
- 239000000047 product Substances 0.000 description 7
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 4
- 229960000359 chromic chloride Drugs 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 230000000875 corresponding effect Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 102000004169 proteins and genes Human genes 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- 208000010470 Ageusia Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 206010022971 Iron Deficiencies Diseases 0.000 description 1
- 206010048259 Zinc deficiency Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000019666 ageusia Nutrition 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 208000007502 anemia Diseases 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 230000037406 food intake Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- MQHUBPZUHMDZNT-UHFFFAOYSA-L zinc;methanedisulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)CS([O-])(=O)=O MQHUBPZUHMDZNT-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/803—Processes of preparation
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
- A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
- A23L33/16—Inorganic salts, minerals or trace elements
- A23L33/165—Complexes or chelates
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/33—Heterocyclic compounds
- A61K31/555—Heterocyclic compounds containing heavy metals, e.g. hemin, hematin, melarsoprol
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
Definitions
- the present invention provides a single-pot process for the preparation of metal picolinates with high purity from alpha picoline, a cheaper raw material.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Public Health (AREA)
- Mycology (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Pharmacology & Pharmacy (AREA)
- Veterinary Medicine (AREA)
- Inorganic Chemistry (AREA)
- Epidemiology (AREA)
- Nutrition Science (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Pyridine Compounds (AREA)
Abstract
The present invention relates to a single pot process for the preparation of metal picolinates useful as dietary supplement from alpha picoline, said process comprising hydrosulphonation of alpha picoline with sulphuric acid; heating the reaction mixture thus obtained between the range of 150° to 210 ° C. followed by oxidation with any suitable oxidizing agent to obtain alpha picolinic acid sulphate, and treating the thus obtained alpha picolinic acid sulphate with a metal salt solution to obtain corresponding metal picolinate.
Description
- The present invention relates to a single-pot process for the preparation of metal picolinates useful as a dietary supplement from alpha picoline source.
- Metal picolinates are finding important place in dietary supplement as the source of physiologically important heavy metals, essential to both humans and animals. Body can not ingest or produce these necessary metals as such and it's deficiency leads to a variety of diseases such as Anemia correlated to iron deficiency, loss of taste and neurophysychiatric symptoms related to zinc deficiency etc. Organometallic compound esp. metallic picolinates are treated to be one of the important sources for metal supplement.
- Earlier, metal picolinates were employed for the treatment of metal deficiencies, U.S. Pat. No. 4,020,158 employs metal picolinates as a food supplement in which hydrolyzed protein products were chelated with metal ions under carefully controlled reaction conditions. N. L. Jenson, U.S. Pat. No. 4,167,564 used hydrolyzed proteins as metal complexes or chelates for administering essential metals in animals. U.S. Pat. No. 4,021,569 uses zinc methionate complex for zinc supplementation.
- The metal compounds with protein derivatives are more effectively assimilated than the elemental or inorganic salt forms. However, the metal co-ordination complexes with picolinic acid are directly available for absorption into the system without competition from other metals. U.S. Pat. No. 4,315,927 outlines processes for manufacturing metal picolinates viz. Iron, copper, Zinc etc. using metal salt and picolinic acid.
- The anionic picolinate moiety acts as a strong chelating agent or ligand capable of binding to a cation. The cation may be a bivalent or trivalent metallic trace element essential to the nutritional value of human or other mammalian species and should exhibit binding capability with picolinic acid. These complexes are intended mainly for oral ingestion where they are generally incorporated in the food material or drinking water. Alternatively, they may be manufactured into tablets or pills with a suitable diluent or pharmaceutically acceptable carrier using any known technique.
- In the prior art of preparing metal picolinates esp. chromium and zinc picolinates, a suitable metal salt namely chromium trichloride and zinc sulphate (U.S. Pat. No. 431,597) is added to a solution of picolinic acid. After the reaction is complete, the precipitated metal complex is filtered and washed with appropriate solvent and dried. U.S. Pat. No. 5,677,461 gives a modified method for producing chromium picolinate from picolinic acid at a relatively lower temperature and appropriate adjustments of pH range than mentioned in U.S. Pat. No. 4,315,927. However both the patents use chromium trichloride and picolinic acid as the starting material for manufacturing chromium picolinate. The starting material i.e. picolinic acid is not easily available. Moreover, the use of chromium trichloride generates chloride ions, which have to be removed by several washings by water or any other suitable solvent. Hence, the process of isolation of the metal picolinate from the reaction mass is cumbersome.
- U.S. Pat. No. 2,513,099 details out a process for oxidizing N− heterocycle compounds containing a pyridine nucleus and an oxidizable organic group attached to the nitrogen containing aromatic nucleus by at least one carbon to carbon linkage. The process involves oxidation by reacting nitric acid with a solution containing the N− heterocycle compound and a mixture of mercury and copper compounds dissolved in sulfuric acid. This process of oxidation may normally lead to the contamination of undesired metals with the required metal picolinates. There is scanty literature available on the oxidation and recovery of the picolinic acid as such.
- Thus there is a need to develop a method for producing metal picolinates from cheap raw materials and by a simpler process.
- The main object of the present invention is to provide a novel single-pot process for the preparation of metal picolinates from alpha picoline source.
- Another object of the present invention is to provide a novel process for oxidation of alpha picoline to picolinic acid with high purity and without any metallic contamination.
- Accordingly, the present invention provides a single-pot process for the preparation of metal picolinates with high purity from alpha picoline, a cheaper raw material.
- Accordingly, the present invention provides a single pot process for the preparation of metal picolinates useful as dietary supplement from alpha picoline, said process comprising hydrosulphonation of alpha picoline with sulphuric acid; heating the reaction mixture thus obtained between the range of 150° to 210° C. followed by oxidation with any suitable oxidizing agent to obtain alpha picolinic acid sulphate, and treating the thus obtained alpha picolinic acid sulphate with a metal salt solution to obtain corresponding metal picolinate.
- More particularly, the present invention provides a process for the preparation of metal picolinates, said process comprising: reacting alpha picoline with sulphuric acid at temperature ranging between 35° to 100° C.; heating the reaction mass to 150° to 210° C.; adding 40 to 70% concentrated Nitric acid to obtain alpha picolinic acid sulphate; adjusting the pH of the solution so as to maintain the pH in the range of 3 to 5; treating the alpha picolinic acid sulphate with a metal salt solution to obtain the corresponding metal picolinate, and purifying the resulting mass to obtain metal picolinates of high purity.
- In an embodiment of the present invention, alpha picoline is alpha picoline (2-methyl pyridine).
- In another embodiment of the present invention, the reaction of alpha picoline with sulphuric acid is carried out at 50° to 90° C.
- In still another embodiment of the present invention, the reaction of alpha picoline with sulphuric acid is carried out at 60° to 80° C.
- In yet another embodiment of the present invention, the reaction mass is heated up to a temperature of 180° to 210° C.
- In still yet another embodiment of the present invention, the reaction mass is heated up to a temperature of 190° to 205° C.
- In yet still another embodiment of the present invention, proper ventilation has to be provided for removal of nitric oxide fumes produced during oxidation.
- In one more embodiment of the present invention, oxidation is carried out for 18 to 22 hours.
- In one another embodiment of the present invention, oxidation is carried out for 20 hours.
- In an embodiment of the present invention, the reaction mixture is cooled to an ambient temperature before adjusting the pH value of the reaction.
- In another embodiment of the present invention, water is added before adjusting the pH value.
- In still another embodiment of the present invention, the pH value is adjusted with the help of standard alkali solutions.
- In yet another embodiment of the present invention, the metal salt used for the preparation of zinc picolinate is selected from the group comprising of zinc sulphate, zinc chloride, zinc acetate and zinc carbonate.
- In still yet another embodiment of the present invention, zinc picolinate having 19 to 22% Zinc content is obtained.
- In yet still another embodiment of the present invention, zinc picolinate having 21% Zinc content is obtained.
- In one more embodiment of the present invention, the metal salt used for the preparation of chromium picolinate is selected from the group comprising of chromium nitrate, chromium chloride, chromium acetate, chromium formate, chromium carbonate and chromium sulphate.
- In one another embodiment of the present invention, chromium picolinate having 12 to 12.6% Chromium content is obtained.
- In an embodiment of the present invention, chromium picolinate having 12.3% Chromium content is obtained.
- In another embodiment of the present invention, pure metal picolinate is obtained by filtering, washing and drying the reaction product.
- In still another embodiment, the present invention provides a scope of utilizing cheaper raw material and an economical single pot synthesis with high purity product. The starting material to prepare the picolinates is alpha picoline (2-methyl pyridine), instead of picolinic acid which has been normally used in the prior arts of the synthesis and which is also much costlier than alpha picoline. Inventors have identified many other chromium salts, which can be used in place of chromium trichloride.
- In yet another embodiment of the present invention, alpha picoline is reacted with sulphuric acid at temperatures ranging from 35° C. to 100° C., preferably between 50° to 90° C. and most preferably between 60° C. to 80° C. Once the addition is over, the reaction mass temperature is increased to 150° C. to 210° C., preferably between 180° to 210° C. and most preferably between 190° C. to 205° C. Nitric acid having 40 to 70% concentration is added slowly. Addition of Nitric acid leads to the evolution of Nitric oxide fume, which has to be properly vented or scrubbed. Reaction mass is then cooled to an ambient temperature and water is added followed by pH adjustment. pH is maintained between 3-5with the help of suitable alkali solution. To the above reaction mass required metal salt solution is added to get the desired metal picolinate. Resulting mass is then filtered washed and dried to get the pure metal picolinate.
- Any one out of the following metal salts can be used for the reaction with alpha picolinic acid sulphate to get the corresponding zinc or chromium picolinates:
- 1. When zinc sulphate, zinc chloride, zinc acetate, zinc carbonates etc. are used the product obtained is zinc picolinate.
- 2. When chromium nitrate, chromium chloride, chromium acetate, chromium formate, chromium carbonate and chromium sulphate etc. are used then the product obtained is chromium picolinate.
- The present invention is further described with the help of the following examples, which are given by way of illustration and therefore should not be construed to limit the scope of the invention in any manner.
- Alpha picoline 1.0 kg was slowly added to concentrated solution of sulphuric acid under agitation. After the addition was completed the mass temperature was raised to 180° C. and 6.0 kg of 70% Nitric acid was added and the temperature was maintained at the same level for 20 hours. After the reaction was over mass was cooled to ambient temperature and three times water was added. pH of the reaction mass was adjusted to 5.0. Zinc sulphate 600 grams dissolved in water was added slowly and the whole mass was stirred till a white precipitate appeared. The precipitate was filtered washed and dried to give 800 grams of zinc picolinate having 21% Zinc content (Desired limit 19-22%)
- Example-1 was repeated following the same procedure but zinc sulphate was replaced by zinc chloride and a product weighing 580 grams having 21.5% zinc content was obtained.
- Picolinic acid sulphate solution (100 grams was dissolved in water 700 ml) was heated to 60°-70° C. and a solution of chromium chloride 30.0 grams was added. The whole mass was heated for 3-6 hrs and cooled to 0°-10° C. Dark red colored precipitate obtained was filtered washed and dried to give 48 grams of red colored product with chromium content 12.3% (desired chromium content 12-12.6%).
- Example-3 was repeated but chromium chloride was replaced by chromium acetate. A pink colored product weighing 41.5 grams of chromium picolinate was isolated with 12.4% chromium content.
Claims (20)
1. A single pot process for the preparation of metal picolinates useful as dietary supplement from alpha picoline, said process comprising hydrosulphonation of alpha picoline with sulphuric acid; heating the reaction mixture thus obtained between the range of 150° to 210° C. followed by oxidation with any suitable oxidizing agent to obtain alpha picolinic acid sulphate, and treating the thus obtained alpha picolinic acid sulphate with a metal salt solution to obtain corresponding metal picolinate.
2. A process as claimed in claim 1 , wherein the said process comprises: reacting alpha picoline with sulphuric acid at temperature ranging between 35° to 100° C.; heating the reaction mass thus obtained to 150° to 210° C.; adding 40 to 70% concentrated Nitric acid to obtain alpha picolinic acid sulphate; adjusting the pH of the solution so as to maintain the pH in the range of 3 to 5; treating the alpha picolinic acid sulphate with metal salt solution to obtain the corresponding metal picolinate; and purifying the resulting mass by any conventional method to obtain metal picolinates of high purity.
3. A process as claimed in any one of claims 1 or 2 wherein alpha picoline is alpha picoline (2-methyl pyridine).
4. A process as claimed in any one of claim 2 , wherein the reaction of alpha picoline with sulphuric acid is carried out at 50° to 90° C.
5. A process as claimed in any one of claim 2 , wherein the reaction of alpha picoline with sulphuric acid is carried out at 60° to 80° C.
6. A process as claimed in any one of claim 2 , wherein the reaction mass is heated up to a temperature of 180° to 210° C.
7. A process as claimed in any one of claim 2 , wherein the reaction mass is heated up to a temperature of 190° C. to 205° C.
8. A process as claimed in any one of claim 2 , wherein nitric oxide fumes produced during oxidation are removed through ventilation.
9. A process as claimed in claim 2 , wherein oxidation is carried out for a time period in the range of 18 to 22 hours.
10. A process as claimed in claim 2 , wherein oxidation is carried out for 20 hours.
11. A process as claimed in claim 2 , wherein the reaction mixture is cooled to an ambient temperature before adjusting the pH value of the reaction.
12. A process as claimed in claim 2 , wherein water is added before adjusting the pH value.
13. A process as claimed in claim 2 , wherein the pH value is adjusted with the help of standard alkali solutions.
14. A process as claimed in claim 2 , wherein the metal salt used for the preparation of zinc picolinates are selected from the group comprising of zinc sulphate, zinc chloride, zinc acetate and zinc carbonate.
15. A process as claimed in claim 2 , wherein zinc picolinate having 19 to 22% Zinc content is obtained.
16. A process as claimed in claim 2 , wherein zinc picolinate having 21% Zinc content is obtained.
17. A process as claimed in claim 2 , wherein the metal salts used for the preparation of chromium picolinates are selected from the group comprising of chromium nitrate, chromium chloride, chromium acetate, chromium formate, chromium carbonate and chromium sulphate.
18. A process as claimed in claim 2 , wherein chromium picolinate having 12 to 12.6% Chromium content is obtained.
19. A process as claimed in claim 2 , wherein chromium picolinate having 12.3% Chromium content is obtained.
20. A process as claimed in claim 2 , wherein the pure metal picolinate is obtained by filtering, washing and drying the reaction product.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| IN606/DEL/2001 | 2001-05-24 | ||
| IN606/01 | 2001-05-24 | ||
| IN606DE2001 | 2001-05-24 |
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| US10/282,210 Continuation-In-Part US7022853B2 (en) | 2001-10-26 | 2002-10-29 | Single pot process for preparing metal nicotinates from beta-picoline |
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| US6486318B1 US6486318B1 (en) | 2002-11-26 |
| US20020177584A1 true US20020177584A1 (en) | 2002-11-28 |
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| US09/983,897 Expired - Fee Related US6486318B1 (en) | 2001-05-24 | 2001-10-26 | Single pot process for preparing metal picolinates from alpha picoline |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US7022853B2 (en) | 2001-10-26 | 2006-04-04 | Jubilant Organosys Ltd. | Single pot process for preparing metal nicotinates from beta-picoline |
| US20160309764A1 (en) * | 2013-12-16 | 2016-10-27 | Nestec S.A. | Food composition comprising ferrous picolinate |
| US12016849B2 (en) * | 2016-10-12 | 2024-06-25 | Bonafide Health, Llc | Magnesium picolinate compositions and methods of use |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US2522163A (en) * | 1950-09-12 | Process of manufacturing | ||
| US2109957A (en) * | 1936-12-18 | 1938-03-01 | Du Pont | Preparation of pyridine-carboxylic acids and the like |
| US2513099A (en) | 1947-09-09 | 1950-06-27 | Allied Chem & Dye Corp | Oxidation of heterocyclic aromatic nitrogen compounds |
| US4021569A (en) | 1973-08-20 | 1977-05-03 | Zinpro Corporation | Method of nutritional supplementation for zinc and methionine by ingesting 1:1 zinc methionine complexes |
| US4167564A (en) | 1974-09-23 | 1979-09-11 | Albion Laboratories, Inc. | Biological assimilation of metals |
| US4020158A (en) | 1975-08-08 | 1977-04-26 | Ashmead H H | Increasing metals in biological tissue |
| US4315927A (en) | 1980-08-08 | 1982-02-16 | The United States Of America As Represented By The Secretary Of Agriculture | Dietary supplementation with essential metal picolinates |
| KR960037692A (en) | 1995-04-13 | 1996-11-19 | 김광희 | New Preparation of Picolinate-Chrome Complex |
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