EP2786135A1 - Sels liquides ioniques de benzylpyridinium et de benzylimidazolinium destinés à être utilisés en chromatographie de surface - Google Patents

Sels liquides ioniques de benzylpyridinium et de benzylimidazolinium destinés à être utilisés en chromatographie de surface

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Publication number
EP2786135A1
EP2786135A1 EP12798677.6A EP12798677A EP2786135A1 EP 2786135 A1 EP2786135 A1 EP 2786135A1 EP 12798677 A EP12798677 A EP 12798677A EP 2786135 A1 EP2786135 A1 EP 2786135A1
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EP
European Patent Office
Prior art keywords
alkyl
group
halo
alkoxy
haloci
Prior art date
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Application number
EP12798677.6A
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German (de)
English (en)
Inventor
Olivier Lavastre
Audrey CABROL
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TotalEnergies One Tech Belgium SA
Centre National de la Recherche Scientifique CNRS
Original Assignee
Total Research and Technology Feluy SA
Centre National de la Recherche Scientifique CNRS
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Application filed by Total Research and Technology Feluy SA, Centre National de la Recherche Scientifique CNRS filed Critical Total Research and Technology Feluy SA
Priority to EP12798677.6A priority Critical patent/EP2786135A1/fr
Publication of EP2786135A1 publication Critical patent/EP2786135A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • 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
    • C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/16—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
    • C07D213/20—Quaternary compounds thereof
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/90—Plate chromatography, e.g. thin layer or paper chromatography

Definitions

  • the present invention is in the field of ionic liquids, chromatography, and polymers technology.
  • ILs ionic liquids
  • Ionic liquids are generally defined as organic salts that are liquid at ambient temperatures, preferably at room temperature.
  • Ionic liquids are composed of large organic cations and small inorganic or organic anions.
  • Room temperature ionic liquids (sometimes abbreviated as RTILs) have emerged as a new class of solvents for practical applications due to their unique combination of low volatility because of their negligible vapor pressure at near ambient temperatures, chemical stability, high thermal stability, high conductivity, wide electrochemical window, wide liquid ranges, ability to dissolve organic and inorganic solutes and gases, and tunable solvent properties.
  • Ionic liquids are actively investigated as alternative solvent media in many industrial applications such as synthesis, catalysis, separation, electrochemistry, or nanoparticles stabilization.
  • ILs may offer some advantage for the processes which require removal of by-products at relatively high temperatures such as polycondensation processes.
  • Another property of ILs is their ability to dissolve several inorganic or organometallic compounds that are used as catalysts in polymerization processes. This offers at least two advantages. Polymerizations in ILs may be conducted under homogeneous conditions otherwise difficult to achieve (an example is a solubility of ATRP catalysts in ILs). Other advantage is a possibility of recycling and reusing solutions of catalyst in I Ls, especially when expensive catalysts (e.g. those based on noble metals) are used.
  • ionic liquids in polymer science is not limited to their application as solvents. Ionic liquids are also used as additives to polymers (plasticizers, components of polymer electrolytes, porogenic agents).
  • ILs Due to the unique properties inherent to ILs, they have also been widely used in various analytical applications including gas chromatography (GC), high-performance liquid chromatography (HPLC), gel permeation chromatography (GPC), liquid-liquid extraction, microextraction, mass spectrometry, and electrophoresis.
  • GC gas chromatography
  • HPLC high-performance liquid chromatography
  • GPC gel permeation chromatography
  • liquid-liquid extraction microextraction
  • mass spectrometry mass spectrometry
  • electrophoresis electrophoresis
  • each ring comprising the nitrogen atom is independently selected from the group consisting of pyridinium, pyrazinium, pyrrolium, imidazolium, pyrazolium, thiazolium, triazolium, indolium, tetrazolium, pyrimidinium, pyridazinium, piperazinium, and piperidinium; each group being optionally substituted with one, two, or three substituents selected from Ci_i 2 alkyl and Ci-i 2 alkoxy;
  • L 1 is Ci-i 2 alkylene; preferably Ci -6 alkylene; more preferably Ci -2 alkylene;
  • L 2 is Ci-i 2 alkylene; preferably Ci -6 alkylene; more preferably Ci -2 alkylene; L 3 is a single bond or Ci-i 2 alkylene; wherein one carbon of the Ci-i 2 alkylene is optionally replaced by one or more heteroatoms; preferably L 3 is a single bond or d. i 2 alkylene;
  • Y 1 is C 6- i 2 aryl substituted with one, two, or three substituents each independently selected from the group consisting of halo, haloCi -6 alkyl, and haloCi -6 alkoxy;
  • Y 2 is C 6- i 2 aryl substituted with one, two, or three substituents each independently selected from the group consisting of halo, haloCi -6 alkyl, and haloCi -6 alkoxy;
  • A is selected from the group consisting of [Br], [CI], [PF 6 ], [AsF 6 ], [SbF 6 ], [N(S0 2 CF 3 ) 2 ], [BF 4 ], [CF3SO3], [CH 3 C0 2 ], [CF 3 S0 2 ], [N0 2 ], [N0 3 ], [CI0 4 ], [I], and [AIR 1 4-n R 2 n ];
  • R 1 is halo or Ci_i 2 alkyl
  • R 2 is halo
  • n is an integer selected from 0, 1 , 2, 3, or 4.
  • These compounds possesses attractive properties as a solvent, in particular as solvent for polymers such as polyolefins. They are suitable as solvent in chemical reactions such as polymerizations as well as for various analytical applications including thin-layer chromatography (TLC), gas chromatography (GC), high-performance liquid chromatography (HPLC), gel permeation chromatography (GPC), liquid-liquid extraction, microextraction, mass spectrometry, and electrophoresis.
  • TLC thin-layer chromatography
  • GC gas chromatography
  • HPLC high-performance liquid chromatography
  • GPC gel permeation chromatography
  • liquid-liquid extraction microextraction
  • mass spectrometry mass spectrometry
  • electrophoresis electrophoresis.
  • halo or halogen as a group or part of a group is generic for fluoro, chloro, bromo or iodo.
  • Ci- 6 alkyl as a group or part of a group defines straight and branched chained saturated hydrocarbon radicals having from 1 to 6 carbon atoms such as, for example, methyl, ethyl, propyl, butyl, 2-methyl-propyl, pentyl, hexyl, 2-methylbutyl, 3-methylpentyl and the like.
  • Ci-i 2 alkyl as a group or part of a group defines straight and branched chained saturated hydrocarbon radicals having from 1 to 12 carbon atoms, such as, those defined for Ci -6 alkyl and heptyl, octyl, 2-methyl-hetyl, 3-ethyl-hexyl, nonyl, decyl, undecanyl, dodecanyl, and the like.
  • Ci-i 2 alkylene as a group or part of a group defines bivalent straight and branched chained saturated hydrocarbon radicals having from 1 to 12 carbon atoms such as, for example, methylene, ethan-1 ,2-diyl, propan-1 ,3-diyl, propan-1 ,2-diyl, butan-1 ,4- diyl, pentan-1 ,5-diyl, hexan-1 ,6-diyl, 2-methylbutan-1 ,4-diyl, 3-methylpentan-1 ,5-diyl, octan-1 ,8-diyl, undecan-1 ,9-diyl, dodecan-1 ,12-diyl, and the like.
  • C 6 -i 2 aryl refers to a polyunsaturated, aromatic hydrocarbyl group having a single ring (i.e. phenyl) or multiple aromatic rings fused together (e.g. naphthyl), or linked covalently, typically containing 6 to 12 atoms; wherein at least one ring is aromatic.
  • Non-limiting examples of C 6- i 2 aryl comprise phenyl, biphenylyl, biphenylenyl, indanyl, or 1 ,2,3,4-tetrahydronaphthyl, or 1 -or 2-naphthanelyl, each of which may be optionally substituted with one, two or three substituents selected from halo, Ci_ 6 alkyl, polyhaloCi -6 alkyl, hydroxy, Ci -6 alkoxy, polyhaloCi -6 alkoxy, Ci- 6 alkoxyCi- 6 alkyl, carboxyl, Ci -6 alkylcarbonyl, Ci -6 alkoxycarbonyl, cyano, nitro, amino, mono- or diCi_ 6 alkylamino, aminocarbonyl, mono- or diCi -6 alkylaminocarbonyl, azido, mercapto.
  • C 1-6 alkoxy or "C 1-6 alkyloxy” as used herein refers to a radical having the Formula -OR a wherein R a is Ci -6 alkyl as defined herein.
  • suitable alkoxy include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert- butoxy, pentyloxy and hexyloxy.
  • haloCi- 6 alkyl refers to an Ci -6 alkyl as defined herein wherein one or more hydrogens are replaced with a halogen, preferably, chloro or fluoro atoms, more preferably fluoro atoms.
  • haloCi -6 alkyl radicals include chloromethyl, 1 -bromoethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 1 ,1 ,1 - trifluoroethyl, 1 -bromopropyl, 2-fluorobutyl, 3,4-difluoropentyl, 3,4,4-trifluoropentyl, 1 ,1 ,1 - trifluorohexyl, and the like.
  • haloCi -6 alkoxy or "haloCi -6 alkyloxy” as used herein refers to a radical having the Formula -OR b wherein R b is haloCi -6 alkyl as defined herein.
  • suitable alkoxys include chloromethoxy, 1 -bromoethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 1 ,1 ,1 -trifluoroethoxy, 1 -bromopropoxy, 2-fluorobutoxy, 3,4- difluoropentyloxy, 3,4,4-trifluoropentyloxy, 1 ,1 ,1 -trifluorohexyloxy, and the like.
  • substituted is used in defining the compounds of the present invention, it is meant to indicate that one or more hydrogens on the atom indicated in the expression using “substituted” is replaced with a selection from the indicated group, provided that the indicated atom's normal valency is not exceeded, and that the substitution results in a chemically stable compound, i.e. a compound that is sufficiently robust to survive isolation to a useful degree of purity from a reaction mixture.
  • chromatography refers to a physical method of separation in which the components to be separated are distributed between two phases, one of which is stationary (stationary phase) while the other (the mobile phase) moves in a definite direction.
  • chromatography includes, among others, the techniques of thin-layer chromatography (TLC), gas chromatography (GC), gel permeation chromatography (GPC), and high-performance liquid chromatography (HPLC).
  • planar chromatography refers to a separation technique in which the stationary phase is present as or on a plane (planar stationary phase).
  • the plane can be a paper, used as such or impregnated by a substrate as the stationary bed (paper chromatography, PC) or a layer of solid particles spread on a support e.g. a glass or metal plate.
  • support or "plate” or “support plate” refers to the plate that supports the stationary phase, such as the thin layer in thin-layer chromatography.
  • TLC thin-layer chromatography
  • stationary phase or “stationary bed” or “sorbent bed” or “absorbent” are used interchangeably and refer to an immobile phase or non-fluid phase employed in the chromatography method.
  • the expression chromatographic bed or sorbent bed may be used as a general term to denote any of the different forms in which the stationary phase is used.
  • the stationary phases used are typically the base sorbents known for chromatographic purposes. These are, for example, silica gel, aluminium oxide, cellulose, kieselguhr or other organic or inorganic polymers or organic/inorganic hybrid polymers.
  • the base sorbents may furthermore be derivatized with functional groups which modify their separation properties.
  • RP phases in which, for example, silica gel has been derivatized with ligands which have C8 or C18 chains (reversed phase material).
  • ligands which have C8 or C18 chains
  • CN or diol-modified phases Suitable common sorbent phases for planar chromatography are described in Klaus K. Unger, Packings and Stationary Phases in Chromatographic Techniques, M. Decker, New York 1990.
  • mobile phase refers to a fluid which migrates through or along the stationary bed, in a definite direction, carrying thereby the sample through the stationary phase. It may be a liquid or a supercritical fluid.
  • exent is also used for the mobile phase.
  • co-eluent refers to a second fluid which migrates through or along the stationary bed, in a definite direction.
  • the co-eluent accompanies the eluent, both forming the mobile phase.
  • additive when referred to polymers means a plasticizer, a component of polymer electrolytes, a porogenic agent, and the like.
  • the present invention relates to a compound formula (I) or (II)
  • each ring comprising the nitrogen atom is independently selected from the group consisting of pyridinium, pyrazinium, pyrrolium, imidazolium, pyrazolium, thiazolium, triazolium, indolium, tetrazolium, pyrimidinium, pyridazinium, piperazinium, and piperidinium, each group being optionally substituted with one, two, or three substituents selected from Ci_i 2 alkyl and Ci-i 2 alkoxy; preferably each ring comprising the nitrogen atom is independently selected from the group consisting of pyridinium, pyrazinium, pyrrolium, imidazolium, pyrazolium, pyrimidinium, pyridazinium, piperazinium, and piperidinium, each group being optionally substituted with one, two, or three substituents selected from Ci_i 2 alkyl and Ci-i 2 alkoxy, preferably optionally substituted with one, two, or three substituent
  • Ci-i 2 alkylene preferably L 1 is Ci -6 alkylene; more preferably L 1 is Ci -3 alkylene; also preferably L 1 is Ci -2 alkylene;
  • Ci-i 2 alkylene preferably L 2 is Ci -6 alkylene; more preferably L 2 is Ci -3 alkylene; also preferably L 2 is Ci -2 alkylene;
  • Ci-i 2 alkylene wherein one carbon of the Ci-i 2 alkylene is optionally replaced by one or more heteroatoms; preferably L 3 is a single bond or Ci -6 alkylene; wherein one carbon of the Ci -6 alkylene is optionally replaced by one or two heteroatoms selected from O, N or S; preferably L 3 is a single bond or Ci -3 alkylene; wherein one carbon of the Ci -3 alkylene is optionally replaced by one heteroatoms selected from O, N or S; preferably L 3 is a single bond or Ci -2 alkylene;
  • A is selected from the group consisting of [Br], [CI], [PF 6 ], [AsF 6 ], [SbF 6 ], [N(S0 2 CF 3 ) 2 ], [BF 4 ], [CF3SO3], [CH 3 C0 2 ], [CF 3 S0 2 ], [N0 2 ], [N0 3 ], [CI0 4 ], [I], and [AIR 1 4-n R 2 n ]; preferably A is selected from the group consisting of [Br], [CI], [PF 6 ], [AsF 6 ], [SbF 6 ],
  • A is selected from the group consisting of [Br], [PF 6 ], [BF 4 ], [CI], [CF 3 SO 3 ], and [I]; preferably A is selected from the group consisting of [Br], [PF 6 ], [BF 4 ];
  • R 1 is halo or Ci-i 2 alkyl; preferably R 1 is halo or Ci -6 alkyl; preferably R 1 is bromo, chloro, iodo, or Ci -4 alkyl;
  • R 2 is halo; preferably R 1 is bromo, or chloro, and
  • n is an integer selected from 0, 1 , 2, 3, or 4.
  • the present invention relates to the compound of formula (I) or (II) as depicted above, preferably of formula (I) wherein
  • each ring comprising the nitrogen atom is independently selected from the group consisting of pyridinium, imidazolium, pyrazinium, pyrrolium, pyrazolium, thiazolium, triazolium, indolium, tetrazolium, pyrimidinium, pyridazinium, piperazinium, and piperidinium; each group being optionally substituted with one, two, or three substituents selected from Ci-i 2 alkyl and Ci-i 2 alkoxy, preferably each group being optionally substituted with one, two, or three substituents selected from Ci -6 alkyl and Ci -6 alkoxy;
  • L 1 is Ci -6 alkylene
  • L 2 is Ci -6 alkylene
  • L 3 is a single bond, or Ci -6 alkylene; wherein one carbon of the Ci -6 alkylene is optionally replaced by one or two heteroatoms;
  • Y 1 is phenyl substituted with one, two, or three substituents selected from the group consisting of halo, haloCi -6 alkyl, and haloCi -6 alkoxy;
  • Y 2 is phenyl substituted with one, two, or three substituents selected from the group consisting of halo, haloCi -6 alkyl, and haloCi -6 alkoxy;
  • A is selected from the group consisting of [Br], [CI], [PF 6 ], [AsF 6 ], [SbF 6 ], [N(S0 2 CF 3 ) 2 ], [BF 4 ], [CF3SO3], [CH 3 C0 2 ], [CF 3 S0 2 ], [N0 2 ], [N0 3 ], [CI0 4 ], [I], and [AIR 1 4-n R 2 n ];
  • R 1 is halo or Ci-i 2 alkyl
  • R 2 is halo
  • n is an integer selected from 0, 1 , 2, 3, or 4.
  • the present invention relates to the compound of formula (I) or (II) as depicted above, preferably (I), wherein
  • each ring comprising the nitrogen atom is independently selected from pyridinium, imidazolium; pyrazinium, and pyrrolium, each being optionally substituted with one, two, or three substituents selected from Ci -6 alkyl and Ci -6 alkoxy, preferably each optionally substituted with one, two, or three substituents selected from Ci -4 alkyl and Ci -4 alkoxy;
  • L 1 is Ci -2 alkylene
  • L 2 is Ci -2 alkylene
  • L 3 is a single bond, or Ci -2 alkylene
  • Y 1 is phenyl substituted with one, two, or three substituents selected from the group consisting of halo, haloCi -6 alkyl, and haloCi -6 alkoxy; preferably halo;
  • Y 2 is phenyl substituted with one, two, or three substituents selected from the group consisting of halo, haloCi -6 alkyl, and haloCi -6 alkoxy; preferably halo;
  • A is selected from the group consisting of [Br], [CI], [PF 6 ], [AsF 6 ], [SbF 6 ], [N(S0 2 CF 3 ) 2 ], [BF 4 ], [CF 3 S0 3 ], [CH 3 C0 2 ], [CF 3 S0 2 ], [N0 2 ], [N0 3 ], [CI0 4 ], [I], and [AIR 1 4-n R 2 n ];
  • R 1 is halo or Ci-i 2 alkyl
  • R 2 is halo
  • n is an integer selected from 0, 1 , 2, 3, and 4.
  • the compound of formula (I) as depicted above is a compound of formula (la), or (lb),
  • A is selected from the group consisting of [Br], [CI], [PF 6 ], [AsF 6 ], [SbF 6 ], [N(S0 2 CF 3 ) 2 ], [BF 4 ], [CF3SO3], [CH 3 C0 2 ], [CF 3 S0 2 ], [N0 2 ], [N0 3 ], [CI0 4 ], [I], and [AIR 1 4-n R 2 n ]; and
  • R 1 is halo or Ci-i 2 alkyl; preferably halo or Ci -6 alkyl;
  • R 2 is halo
  • n is an integer selected from 0, 1 , 2, 3, or 4;
  • L 1 is Ci -6 alkylene; preferably L 1 is Ci -4 alkylene; preferably L 1 is Ci -2 alkylene; preferably - CH 2 -;
  • each R 3 is independently selected from hydrogen, Ci -6 alkyl and Ci -6 alkoxy;
  • each R 4 is independently selected from the group consisting of halo, haloCi -6 alkyl, and haloCi -6 alkoxy;
  • R 5 is independently selected from Ci -6 alkyl or hydrogen; preferably Ci -6 alkyl;
  • p is an integer selected from 1 , 2, or 3;
  • q is an integer selected from 1 , 2, or 3.
  • the ionic liquid is a compound of formula (la), or (lb), as depicted above, wherein A is selected from the group consisting of [Br], [CI], [PF 6 ], [AsF 6 ], [SbF 6 ], [BF 4 ], [CH 3 C0 2 ], [CF 3 S0 2 ], [N0 2 ], [N0 3 ], [CI0 4 ], [I];
  • L 1 is Ci -6 alkylene; preferably L 1 is Ci -4 alkylene; more preferably L 1 is Ci -2 alkylene; preferably -CH 2 -;
  • each R 3 is independently selected from hydrogen, Ci -6 alkyl and Ci -6 alkoxy;
  • each R 4 is independently selected from the group consisting of halo, haloCi -6 alkyl, and haloCi -6 alkoxy;
  • R 5 is independently selected from Ci -6 alkyl or hydrogen; preferably Ci -6 alkyl;
  • p is an integer selected from 1 , 2, or 3;
  • q is an integer selected from 1 , 2, or 3.
  • the ionic liquid is a compound of formula (la), or (lb), as depicted above, wherein
  • A is selected from the group consisting of [Br], [CI], [PF 6 ], [BF 4 ], [CH 3 C0 2 ], [CF 3 S0 2 ], [I];
  • L 1 is Ci -4 alkylene; more preferably L 1 is Ci -2 alkylene; preferably -CH 2 -;
  • each R 3 is independently selected from hydrogen, Ci -6 alkyl and Ci -6 alkoxy;
  • each R 4 is independently selected from the group consisting of halo, haloCi -6 alkyl, and haloCi -6 alkoxy;
  • R 5 is independently selected from Ci -6 alkyl or hydrogen; preferably Ci -6 alkyl;
  • p is an integer selected from 1 , 2, or 3;
  • q is an integer selected from 1 , 2, or 3.
  • the ionic liquid is a compound of formula (la), or (lb), as depicted above, wherein
  • A is selected from the group consisting of [Br], [CI], [PF 6 ], and [BF 4 ];
  • L 1 is Ci -4 alkylene; more preferably L 1 is Ci -2 alkylene; preferably -CH 2 -;
  • each R 3 is independently selected from hydrogen, Ci -6 alkyl and Ci -6 alkoxy;
  • each R 4 is independently selected from the group consisting of halo, haloCi -6 alkyl, and haloCi -6 alkoxy;
  • R 5 is independently selected from Ci -6 alkyl or hydrogen; preferably Ci -6 alkyl;
  • p is an integer selected from 1 , 2, or 3; and q is an integer selected from 1 , 2, or 3.
  • the ionic liquid is a compound of formula (la), or (lb), as depicted above, wherein
  • A is [Br], [PF 6 ], [BF 4 ];
  • L 1 is Ci -2 alkylene; preferably -CH 2 -;
  • each R 3 is independently selected from hydrogen, Ci -4 alkyl and Ci -4 alkoxy; preferably hydrogen
  • each R 4 is independently selected from chloro, fluoro, and bromo, preferably chloro or, bromo,
  • R 5 is independently selected from Ci -4 alkyl or hydrogen; preferably Ci -2 alkyl;
  • p 1 , 2 or 3
  • q is 1 , 2, or 3.
  • the ionic liquid is a compound of formula (la), or (lb) as depicted above, wherein
  • A is Br], [PF 6 ], or [BF 4 ],
  • L 1 is Ci -2 alkylene; preferably -CH 2 -;
  • each R 3 is hydrogen, or Ci -4 alkyl
  • each R 4 is independently selected from chloro or bromo, and
  • R 5 is independently selected from Ci -2 alkyl or hydrogen ;
  • p 1 , 2 or 3
  • q is 1 , 2, or 3.
  • the ionic liquid is a compound of formula (la), or (lb) as depicted above, wherein
  • A is [Br], [PF 6 ], [BF 4 ];
  • L 1 is Ci -2 alkylene; preferably -CH 2 -;
  • each R 3 is hydrogen, or Ci -4 alkyl; preferably hydrogen
  • each R 4 is independently selected from chloro, and bromo,
  • R 5 is independently selected from Ci -2 alkyl or hydrogen ; preferably Ci -2 alkyl; p is 1 , or 2, and
  • q is 1 , 2, or 3.
  • the ionic liquid is a compound of formula (la), or (lb) as depicted above, wherein
  • A is [Br], [PF 6 ], [BF 4 ];
  • L 1 is Ci -2 alkylene; preferably -CH 2 -;
  • each R 3 is hydrogen
  • each R 4 is independently selected from chloro, and bromo,
  • R 5 is independently selected from Ci -2 alkyl or hydrogen ; preferably Ci -2 alkyl;
  • the ionic liquid is a compound as listed in Table 1 .
  • the present invention further relates to the use of a compound of formula (I), (II), (la), or (lb) as a solvent; preferably as a solvent for polymers.
  • the present invention further relates to the use of a compound of formula (I), (II), (la), or (lb) as an eluent; preferably as an eluent for polymers.
  • the polymers are selected from the group comprising polyolefins, polyamides, polycarbonates, poly(hydroxy carboxylic acid) , polystyrenes, polyesters, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polymethylmethacrylate (PMMA), poly(methyl acrylate) (PMA), vinyl polymers, proteins, and polysaccharides, or blends thereof.
  • the compound of formula (I), (II), (la), or (lb), is particularly useful as a solvent or as an eluent for polyolefins.
  • the polyolefins may be any olefin homopolymer or any copolymer of an olefin and one or more comonomers.
  • the polyolefins may be atactic, syndiotactic or isotactic.
  • the olefin can for example be ethylene, propylene, 1 -butene, 1 -pentene, 1 -hexene, 4-methyl-1 -pentene or 1 -octene, but also cycloolefins such as for example cyclopentene, cyclohexene, cyclooctene or norbornene.
  • the comonomer may be different from the olefin and chosen such that it is suited for copolymerization with the olefin.
  • the comonomer may be an olefin as defined above.
  • olefin copolymers that can be analyzed, separated, or characterized in the present invention are random copolymers of propylene and ethylene, random copolymers of propylene and 1 -butene, heterophasic copolymers of propylene and ethylene, ethylene- butene copolymers, ethylene-hexene copolymers, ethylene-octene copolymers, copolymers of ethylene and vinyl acetate (EVA), copolymers of ethylene and vinyl alcohol (EVOH).
  • polyolefins are olefin homopolymers and copolymers of an olefin and optionally one or more comonomers, wherein said olefin and said one or more comonomer are different.
  • said olefin is ethylene or propylene.
  • the term "comonomer” refers to olefin comonomers which are suitable for being polymerized with olefin monomers, preferably ethylene or propylene monomers.
  • Comonomers may comprise but are not limited to aliphatic C 2 -C 2 o alpha-olefins.
  • Suitable aliphatic C 2 -C 20 alpha-olefins include ethylene, propylene, 1 -butene, 4-methyl-1 -pentene, 1 -hexene, 1 -octene, 1 -decene, 1 -dodecene, 1 -tetradecene, 1 -hexadecene, 1 -octadecene and 1 -eicosene.
  • Preferred polyolefins for use in the present invention are propylene and ethylene polymers.
  • the terms "propylene polymer” and “polypropylene” as well as the terms "ethylene polymer” and “polyethylene” are used interchangeably.
  • the polyolefin is selected from polyethylene and polypropylene homo- and copolymers.
  • the present invention further relates to a chromatographic stationary phase impregnated with the ionic liquid compound of formula (I), (II), (la), or (lb), according to any one of the embodiments presented herein.
  • the present invention also encompasses a composition for use in chromatography comprising a substrate impregnated with an ionic liquid of formula (I), (II), (la), or (lb).
  • the impregnation of the stationary phase with an ionic liquid of formula (I), (II), (la), or (lb) may be performed by simply pouring, mixing or spraying the ionic liquid pure or in solution onto the stationary phase, and optionally allowing the stationary phase to dry.
  • the impregnation may be performed by covalent anchoring of non- coordinating anions on mineral supports to prepare supported ionic liquids as described in US201 1/0178258.
  • the substrate comprises silica based normal and reverse-phase resin optionally derivatized with alkyl groups or aromatic groups, preferably silica gel 60F254.
  • One embodiment of the present invention relates to the use of a composition according to the present invention as a stationary phase in chromatography.
  • One embodiment of the present invention relates to a method of performing chromatography characterized in that the stationary phase is a composition according to the present invention.
  • the chromatography is a planar chromatography.
  • One embodiment of the present invention relates to a method of performing chromatography characterized in that the stationary phase is a composition according to the present invention, in a method for analyzing, separating, or characterizing chemical compounds, preferably polymers selected from polyolefins, polyamides, polycarbonates, poly(hydroxy carboxylic acid) like polylactic acid, polystyrenes, polyesters polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polymethylmethacrylate (PMMA), poly(methyl acrylate) (PMA), vinyl polymers, proteins, and polysaccharides; or blends thereof.
  • the present invention also relates to a method of performing planar chromatography characterized in that the planar stationary phase is impregnated with an ionic liquid of formula (I), (II), (la), or (lb) .
  • the present invention also relates to the use of a compound of formula (I), (II), (la), or (lb) as defined in any one of the embodiments presented herein, as a mobile phase in chromatography.
  • the present invention also relates to the use of a compound of formula (I), (II), (la), or (lb) as defined in any one of the embodiments presented herein, as an eluent in chromatography.
  • the present invention further relates to the use of a compound of formula (I), (II), (la), or (lb) as defined in any one of the embodiments presented herein, as a co-eluent in chromatography.
  • the present invention further relates to the use of a compound of formula (I), (II), (la), or (lb) as defined in any one of the embodiments presented herein, as a solvent in a chemical reaction.
  • the present invention further relates to the use of a compound of formula (I), (II), (la), or (lb) as defined in any one of the embodiments presented herein, as a solvent in a chemical separation such as liquid-liquid extraction, microextraction, and electrophoresis, or in mass spectrometry.
  • the chemical reaction is selected from a polycondensation, a polymerization, a radical polymerization, and an ionic polymerization.
  • the present invention further relates to the use of a compound of formula (I), (II), (la), or (lb) as defined in any one of the embodiments presented herein, as an additive to polymers.
  • the additive to polymers is selected from a plasticizer, a component of polymer electrolytes, and a porogenic agent.
  • the present invention further relates to a method for the preparation of the ionic liquid compound of formula (I) or (II) as defined in any one of the embodiments presented herein, comprising contacting a compound of formula (Ig) with a compound of formula (Ih) thereby forming the compound of formula (I)
  • X 1 is halo
  • the nitrogen-containing ring is selected from the group consisting of pyridine, imidazole, pyrazine, pyrrole, pyrazole, thiazole, triazole, indole, tetrazole, pyrimidine, pyridazine, piperazine, and piperidine; each group being optionally substituted with one, two, or three substituents selected from Ci_i 2 alkyl and Ci-i 2 alkoxy; and L 1 , and Y 1 are as defined in any one of the embodiments presented herein.
  • the contacting step can be done at room temperature in a suitable solvent such as ethyl acetate.
  • the two solutions were mixed and a white precipitate was immediately formed.
  • the aqueous solution containing the precipitate was extracted several times with dichloromethane.
  • the organic phases were combined, washed several time with water and subsequently dried using magnesium sulfate.
  • the dichloromethane was removed under vacuum and 94 mg (yield:45%) of a white solid was obtained having a melting point of 139.48°C.
  • the two solutions were mixed and a white precipitate was immediately formed.
  • the aqueous solution containing the precipitate was extracted several times with dichloromethane.
  • the organic phases were combined, washed several time with water and subsequently dried using magnesium sulfate.
  • the dichloromethane was removed under vacuum and 231 mg (yield:17%) of a white solid was obtained having a melting point of 164°C.
  • the two solutions were mixed and a white precipitate was immediately formed.
  • the aqueous solution containing the precipitate was extracted several times with dichloromethane.
  • the organic phases were combined, washed several time with water and subsequently dried using magnesium sulfate.
  • the dichloromethane was removed under vacuum and 3.28 g (yield:91 %) of a white solid was obtained having a melting point of 163.92°C.
  • Ionic liquid 7 Two solutions were prepared:
  • the two solutions were mixed and a white precipitate was immediately formed.
  • the aqueous solution containing the precipitate was extracted several times with dichloromethane.
  • the organic phases were combined, washed several time with water and subsequently dried using magnesium sulfate.
  • the dichloromethane was removed under vacuum and a white solid was obtained having a melting point of 180°C.
  • the ionic liquids as listed in Table 2 have been tested as solvent for polyethylene.
  • the polyethylenes were dissolved in all the tested ionic liquids (results not shown).

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Abstract

L'invention porte sur un composé liquide ionique de formule (I) ou (II), dans laquelle chaque noyau comprenant l'atome d'azote est indépendamment choisi dans le groupe constitué par les noyaux pyridinium, imidazolium, pyrazinium, pyrrolium, pyrazolium, thiazolium, triazolium, indolium, tétrazolium, pyrimidinium, pyridazinium, pipérazinium et pipéridinium ; chaque groupe étant éventuellement substitué par un, deux ou trois substituants choisis parmi les substituants alkyle en C1-12 et alcoxy en C1-12 ; L1 représente un groupe alkylène en C1-12 ; L2 représente un groupe alkylène en C1-12 ; L3 représente une simple liaison ou un groupe alkylène en C1-12, un carbone du groupe alkylène en C1-12 étant éventuellement remplacé par un ou plusieurs hétéroatomes ; Y1 représente un groupe aryle en C6-12 substitué par un, deux ou trois substituants chacun indépendamment choisis dans le groupe constitué par les substituants halogéno, halogénoalkyle en C1-6 et halogénoalcoxy en C1-6 ; Y2 représente un groupe aryle en C6-12 substitué par un, deux ou trois substituants chacun indépendamment choisis dans le groupe constitué par les substituants halogéno, halogénoalkyle en C1-6 et halogénoalcoxy en C1-6 ; A est choisi dans le groupe constitué par [Br], [Cl], [PF6], [AsF6], [SbF6], [N(SO2CF3)2], [BF4], [CF3SO3], [CH3CO2], [CF3SO2], [NO2], [NO3], [ClO4], [I] et [AlR1 4-nR2 n] ; R1 représente un atome d'halogène ou un groupe alkyle en C1-12 ; R2 représente un atome d'halogène ; et n représente un nombre entier choisi parmi 0, 1, 2, 3 ou 4. L'invention porte en outre sur des utilisations des composés liquides ioniques de l'invention ainsi que sur des procédés pour leur préparation.
EP12798677.6A 2011-11-29 2012-11-29 Sels liquides ioniques de benzylpyridinium et de benzylimidazolinium destinés à être utilisés en chromatographie de surface Withdrawn EP2786135A1 (fr)

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EP12798677.6A EP2786135A1 (fr) 2011-11-29 2012-11-29 Sels liquides ioniques de benzylpyridinium et de benzylimidazolinium destinés à être utilisés en chromatographie de surface
PCT/EP2012/074000 WO2013079616A1 (fr) 2011-11-29 2012-11-29 Sels liquides ioniques de benzylpyridinium et de benzylimidazolinium destinés à être utilisés en chromatographie de surface

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ES2524494T3 (es) 2014-12-09
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EP2643686A1 (fr) 2013-10-02
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