WO2004101524A1 - Esters polyglyceroliques d'acides pyridinecarboxyliques - Google Patents

Esters polyglyceroliques d'acides pyridinecarboxyliques Download PDF

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Publication number
WO2004101524A1
WO2004101524A1 PCT/EP2004/005271 EP2004005271W WO2004101524A1 WO 2004101524 A1 WO2004101524 A1 WO 2004101524A1 EP 2004005271 W EP2004005271 W EP 2004005271W WO 2004101524 A1 WO2004101524 A1 WO 2004101524A1
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WO
WIPO (PCT)
Prior art keywords
polyglycerol
acid
esterification
pyridinecarboxylic
titanium
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Application number
PCT/EP2004/005271
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English (en)
Inventor
Eddy Bruchez
Larry K. Hall
Cornelia Zur
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Lonza Ag
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Publication of WO2004101524A1 publication Critical patent/WO2004101524A1/fr

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/04—Saturated ethers
    • C07C43/13—Saturated ethers containing hydroxy or O-metal groups
    • C07C43/135—Saturated ethers containing hydroxy or O-metal groups having more than one ether bond
    • 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
    • C07D213/80—Acids; Esters in position 3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
    • C08G65/3328—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof heterocyclic

Definitions

  • the present invention refers to polyglycerol esters of pyridinecarboxylic acids and to a process for their preparation as well as to a titanium catalyst and its use in a process for the preparation of polyglycerol esters.
  • polyglycerol esters of pyridinecarboxylic acids examples include polyglycerol esters of nicotinic acid.
  • Polyglycerol esters of nicotinic acid can be used as additives for liquid animal feed, since they are easily water-soluble and are hydrolyzed to the starting materials nicotinic acid and non-toxic polyglycerol.
  • esters of glycerol with pyridinecarboxylic acids are known in the art.
  • the process of the present invention for the preparation of polyglycerol esters of pyridinecarboxylic acids comprises the step of esterifying a polyglycerol with a pyridinecarboxylic acid.
  • Polyglycerols are compounds composed of condensed glycerol units. Condensation in this context is to be understood to be the reaction of two OH groups under formation of an ether bond and loss of one molecule of water. Polyglycerols can be either pure polyglycerols of unique molecular weight or mixtures of polyglycerols of different molecular weights. A pure polyglycerol of unique molecular weight can consist either of one isomer or of a mixture of isomers.
  • Examples of pure polyglycerols are diglycerol, triglycerol, tetraglycerol, pentaglycerol, hexaglycerol, heptaglycerol, octaglycerol, nonaglycerol, decaglycerol, undecaglycerol, dodecaglycerol, pentadecaglycerol, eicosaglycerol, pentacosaglycerol and triacontaglycerol.
  • Polyglycerols can be characterized by their OH value.
  • the OH value is defined as the number of milligrams of potassium hydroxide required to neutralize the acetic acid needed to acetylate 1 g of polyglycerol.
  • OH values of some polyglycerols are as follows: 1352 for diglycerol, 1071 for tetraglycerol, 970 for hexaglycerol, 920 for octaglycerol, 888 for decaglycerol, 825 for eicosaglycerol and 802 for triacontaglycerol.
  • polyglycerol is a polyglycerol having an OH value of 1352 to 888. More preferably, polyglycerol is a polyglycerol having an OH value of 1071 to 920. Most preferably, polyglycerol is a polyglycerol having an OH value of 970 ⁇ 42 and a mean molecular weight of 462 ⁇ 74 g/mol.
  • Polyglycerols can be obtained by condensing glycerol in the presence of sodium hydroxide at temperatures of 180 to 265 °C and distilling off the water formed during the reaction, as described in US 2,258,892 and US 3,637,774.
  • Polyglycerols can be obtained by chromatographic separation of mixtures of polyglycerols, as described in US 5,431,822.
  • Pyridinecarboxylic acids are picolinic acid (2-pyridinecarboxylic acid), nicotinic acid (3 -pyridinecarboxylic acid) and isonicotinic acid (4-pyridinecarboxylic acid).
  • the pyridinecarboxylic acid is nicotinic acid or isonicotinic acid. Most preferably, it is nicotinic acid.
  • Picolinic acid, nicotinic acid and isonicotinic acid are commercially available.
  • Polyglycerol esters of pyridinecarboxylic acids result from esterification of some or all of the hydroxyl groups of a polyglycerol with a pyridinecarboxylic acid.
  • the definitions of polyglycerols and pyridinecarboxylic acids given above apply accordingly to polyglycerol esters of pyridinecarboxylic acids.
  • polyglycerol esters of pyridinecarboxylic acids result from esterification of 5 to 95%, more preferably of 5 to 50%, most preferably of 10 to 25%, of the hydroxyl groups of a polyglycerol with a pyridinecarboxylic acid.
  • the polyglycerol esters of pyridinecarboxylic acids have a water content of 15% to 80%) (w/w), more preferably of 15 to 60% (w/w), most preferably of 15 to 40% (w/w).
  • water-free samples of polyglycerol esters of pyridinecarboxylic acids obtained by complete removal of the water, e.g. by distillation have a content of polyglycerol ester of pyridine carboxylic acid of at least 50% (w/w), more preferably of at least 55% (w/w), most preferably of at least 60% (w/w).
  • Polyglycerols employed in the esterification can contain up to 40% (w/w) water, preferably they contain less than 20% (w/w) water, more preferably they contain less than 10% (w/w) water, most preferably they contain less than 5% (w/w) water.
  • Any molar ratio of polyglycerol to pyridinecarboxylic acid can be employed.
  • a ratio of polyglycerol to pyridinecarboxylic acid is employed that theoretically results in the esterification of 5 to 95% of the OH groups of the polyglycerol. More preferably, a ratio of polyglycerol to pyridinecarboxylic acid is employed that theoretically results in the esterification of 5 to 50% of the OH groups of the polyglycerol. Most preferably, a ratio of polyglycerol to pyridinecarboxylic acid is employed that theoretically results in the esterification of 10 to 25% of the OH groups of the polyglycerol. Preferably, water is removed by distillation during the esterification.
  • the esterification can be carried out at a temperature of 80 to 260 °C. Preferably, it is carried out at a temperature of 120 to 200 °C, more preferably at 140 to 180 °C. Most preferably, it is carried out at a temperature of 150 to 170 °C.
  • the esterification can be carried out either without additional solvent or in the presence of an organic solvent, in particular in the presence of an organic solvent forming an azeo- trope with water.
  • organic solvents forming an azeotrope with water are o-xylene, m-xylene, -xylene, toluene, benzene, heptane, octane, decane, cyclohexane, methylcyclohexane, ethyl acetate, butyl acetate, propyl acetate, dioxane, dibutyl ether, diisopropyl ether and diethoxyethane.
  • the esterification is carried out without additional solvent or in the presence of an organic solvent selected from the group consisting of o-xylene, -xylene, p-xylene, butyl acetate and diethoxyethane.
  • an organic solvent selected from the group consisting of o-xylene, -xylene, p-xylene, butyl acetate and diethoxyethane.
  • the esterification can be carried out at atmospheric pressure or under (partial) vacuum, wherein the vacuum can be applied intermittently or constantly. Preferably, it is carried out under intermittent or constant vacuum of less than 400 mbar. More preferably, it is carried out under intermittent or constant vacuum of less than 250 mbar.
  • the esterification can be carried out with or without catalyst.
  • Suitable catalysts are selected from the group consisting of mineral acids, organic sulfonic acids, metal salts and metal oxides.
  • mineral acids are hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid and hypo- phosphorous acid.
  • organic sulfonic acids are methanesulfonic acid and ?-toluenesulfonic acid.
  • metal salts are lithium perchlorate, sodium hydroxide, sodium sulfate, sodium hydrogen sulfate, magnesium bromide, titanium sulfate, titanium(iv) butoxide, titanium(iv) butoxide cross-linked with glycerol, ferric chloride, and tin tetrachloride.
  • metal oxides are titanium oxide, zirconium oxide and zinc oxide.
  • the esterification is carried in the presence of a metal salt or a metal oxide. More preferably, the esterification is carried out in the presence of a titanium salt. Most preferably, it is carried out in the presence of titanium(iv) butoxide cross-linked with glycerol.
  • the reaction mixture is preferably worked-up by diluting the reaction mixture with at least 15% (w/w) of water, removing solid catalysts that are present, and treating the reaction mixture with at least one material selected from the group consisting of cation exchange resins, anion exchange resins, activated charcoal and Celite ® .
  • the material selected from the group consisting of cation exchange resins, anion ex- change resins, activated charcoal and Celite ® can be removed, e.g. by filtration.
  • the reaction mixture is worked-up by diluting the reaction mixture with at least 15% (w/w) of water, removing any solid catalysts that are present, and treating the reaction mixture with activated charcoal.
  • the water content of the reaction mixture is preferably adjusted to 15 to 80% (w/w), more preferably to 15 to 60% (w/w), most preferably to 15 to 40% (w/w) by either addition or removal, e.g. by distillation, of water.
  • Another object of the invention are polyglycerol esters of pyridinecarboxylic acids obtainable by the process of the present invention. All definitions given above for the process of the present invention apply accordingly.
  • Still another object of the invention is titanium(iv) butoxide cross-linked with glycerol, obtainable by reacting titanium(iv) butoxide with glycerol, and its use in a process for the preparation of polygycerol esters.
  • Polyglycerol esters result from esterification of some or all of the hydroxyl groups of a polyglycerol with any organic carboxylic acid.
  • the above definition of polyglycerol applies accordingly to polyglycerol esters.
  • organic carboxylic acids are fatty acids, (hetero-) aromatic acids and saturated acyclic C 2 _ 8 -aliphatic acids.
  • fatty acids are palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid and arachidonic acid.
  • Examples of (hetero-) aromatic carboxylic acids are benzoic acid and pyridinecarboxylic acids. Pyridinecarboxylic acids are as defined above.
  • saturated acyclic C 2 _ 8 -aliphatic acids are acetic acid, propiomc acid, butyric acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid and isomers thereof.
  • polyglycerol ester result from esterification of some or all of the hydroxyl groups of a polyglycerol with an organic carboxylic acid selected from the group consisting of fatty acids and aromatic acids, more preferably with a pyridinecarboxylic acid, most preferably with nicotinic acid.
  • Aqueous potassium hydroxide solution (45% (w/w) potassium hydroxide, 82.7 kg) was added to glycerol (99% (w/w) glycerol, 6803.9 kg). The reaction mixture was heated to
  • Nicotinic acid (100%, 24.62 g, 0.200 mol) and o-xylene (159 g) were added to polyglycerol (85.0% (w/w) polyglycerol having an OH value of 965 and an average molecular weight of 462 g/mol, 54.41 g, 0.100 mol) obtained as described in Example 1.
  • the reaction mixture was heated to 140 °C and water was removed by distillation. After 123 h, the reaction mixture was cooled to 80 °C, diluted with 1160% (w/w) water and treated with 250% (w/w) tetrahydrofuran-washed basic anion exchange resin (Lewatit ® MonoPlus M 500, chloride form) at room temperature for 1 h.
  • a water-free sample obtained by complete removal of water contained 85% (w/w) polyglycerol ester of nicotinic acid having ca. 20% of the hydroxyl groups esterified, 0% (w/w) nicotinic acid and 15% (w/w) polyglycerol.
  • Nicotinic acid (100%, 98.45 g, 0.800 mol) was added to polyglycerol (85% (w/w) polyglycerol having an OH value of 965 and an average molecular weight of 462 g/mol, 217.64 g, 0.400 mol) obtained as described in Example 1.
  • the reaction mixture was heated to 160 °C and water was removed by distillation by constantly applying a vacuum of 250 mbar. After 28 h, the reaction mixture was diluted with 5000% (w/w) water and treated with 50% (w/w) tetrahydrofuran-washed basic anion exchange resin (Amberlite ® IRA 900, OH form) at room temperature for 1 h.
  • a water-free sample obtained by complete removal of water contained 63% (w/w) polyglycerol ester of nicotinic acid having ca. 14% of the hydroxyl groups esterified, 1.5% (w/w) nicotinic acid and 36% (w/w) polyglycerol.
  • Polyglycerol (85% (w/w) polyglycerol having an OH value of 965 and an average molecular weight of 462 g/mol, 553.2 g, 1.000 mol) obtained as described in Example 1 was heated to 140 °C and water was distilled off using a water separator by slowly applying a vacuum of 150 mbar. The vacuum was broken and nicotinic acid (100%, 123.1 g, 1.000 mol) was added. The reaction mixture was heated to 160 °C and a vacuum of 100 mbar was applied intermittently in order to distil water.
  • a water-free sample obtained by complete removal of water contained 69% (w/w) polyglycerol ester of nicotinic acid having ca. 16% of the hydroxyl groups esterified, 3.5% (w/w) nicotinic acid and 28% (w/w) polyglycerol.
  • Polyglycerol (83.6% (w/w) polyglycerol having an OH value of 965 and an average molecular weight of 463 g/mol, 221.20 g, 0.400 mol) obtained in analogy to the method as described in Example 1 was heated to 140 °C and water was distilled using a water separator by slowly applying a vacuum of 150 mbar. The vacuum was broken and titanium(iv) butoxide cross-linked with glycerol (100%, 10.40 g, 0.024 mol) obtained as described in example 5 and nicotinic acid (100%, 49.23 g, 0.400 mol) were added. The reaction mixture was heated to 160 °C and a vacuum of 100 mbar was applied intermittently in order to distil water.
  • the filtrate was treated with 5% (w/w) activated charcoal at reflux for 2 h. After removal of charcoal by filtration, the filtrate was concentrated in vacuo to yield 236.6 g of a dark yellowish to brownish viscous oil having a water content of 24.7% (w/w).
  • a water-free sample obtained after complete removal of water contained 71% (w/w) polyglycerol nicotinic acid ester having 16% of the hydroxyl groups esterified, 2.6% (w/w) nicotinic acid and 26% (w/w) polyglycerol.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyethers (AREA)

Abstract

L'invention concerne des esters polyglycéroliques d'acides pyridinecarboxyliques. Pour préparer ces esters, on estérifie un polyglycérol avec un acide pyridinecarboxylique.
PCT/EP2004/005271 2003-05-19 2004-05-17 Esters polyglyceroliques d'acides pyridinecarboxyliques WO2004101524A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US47135003P 2003-05-19 2003-05-19
US60/471,350 2003-05-19
EP03016874 2003-07-24
EP03016874.4 2003-07-24

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WO2004101524A1 true WO2004101524A1 (fr) 2004-11-25

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5385920A (en) * 1992-06-10 1995-01-31 Adir Et Compagnie Diacylglycerol nicotinates
WO2002036534A2 (fr) * 2000-11-06 2002-05-10 Lonza Inc. Procedes de preparation de polyglycerols et d'esters polyglyceroliques lineaires
WO2002066433A1 (fr) * 2001-02-19 2002-08-29 Lonza Ag Procede et catalyseur de preparation d'acetylpyridines

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5385920A (en) * 1992-06-10 1995-01-31 Adir Et Compagnie Diacylglycerol nicotinates
WO2002036534A2 (fr) * 2000-11-06 2002-05-10 Lonza Inc. Procedes de preparation de polyglycerols et d'esters polyglyceroliques lineaires
WO2002066433A1 (fr) * 2001-02-19 2002-08-29 Lonza Ag Procede et catalyseur de preparation d'acetylpyridines

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
BADGETT C O ET AL: "NICOTINIC ACID MISCELLANEOUS ESTERS", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, AMERICAN CHEMICAL SOCIETY, WASHINGTON, DC, US, vol. 69, November 1947 (1947-11-01), pages 2907, XP000995349, ISSN: 0002-7863 *
ROHRBACH, P. ET AL: "Nicotinic acid and various derivatives as hypolipemia-producing compounds", THERAPIE , 21(4), 1063-73 CODEN: THERAP; ISSN: 0040-5957, 1966, XP009036311 *
SUGIHARA, JUKO ET AL: "Studies on intestinal lymphatic absorption of drugs. II. Glyceride prodrugs for improving lymphatic absorption of naproxen and nicotinic acid", JOURNAL OF PHARMACOBIO-DYNAMICS , 11(8), 555-62 CODEN: JOPHDQ; ISSN: 0386-846X, 1988, XP009036312 *

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