WO2002079212A1 - Phosphonium phosphinate compounds and their preparation - Google Patents

Phosphonium phosphinate compounds and their preparation Download PDF

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Publication number
WO2002079212A1
WO2002079212A1 PCT/US2002/006104 US0206104W WO02079212A1 WO 2002079212 A1 WO2002079212 A1 WO 2002079212A1 US 0206104 W US0206104 W US 0206104W WO 02079212 A1 WO02079212 A1 WO 02079212A1
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Prior art keywords
phosphonium
tetradecyl
trihexyl
compound
formula
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PCT/US2002/006104
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English (en)
French (fr)
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Allan James Robertson
Kenneth Richard Seddon
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Cytec Canada Inc.
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Priority to US10/473,271 priority Critical patent/US20040106823A1/en
Priority to EP02707923A priority patent/EP1373280A1/en
Priority to BR0208199-7A priority patent/BR0208199A/pt
Priority to KR10-2003-7012520A priority patent/KR20030093282A/ko
Publication of WO2002079212A1 publication Critical patent/WO2002079212A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/54—Quaternary phosphonium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
    • C07B37/04—Substitution
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • Ionic liquids provide an attractive potential alternative to traditional organic solvents for chemical reactions for many reasons.
  • the low vapour pressure of ionic liquids is a very important feature. They are essentially non-volatile, a property that eliminates many of the containment problems typically encountered with traditional organic solvents. Since ionic liquids are often composed of poorly coordinating ions, they have the potential to provide a highly polar yet poorly coordinating solvent. Moreover, many of these solvents are immiscible with traditional organic solvents and therefore provide a non-aqueous polar alternative to two-phase systems.
  • Ionic liquids provide solvents with a wide liquid range and a high degree of thermal stability. However, there remains a need for increasing the solvent options available to chemists by developing novel ionic liquids with distinctive physical and chemical properties.
  • the current invention provides novel phosphonium phosphinate compounds and methods of preparing these compounds.
  • the phosphonium phosphinate compounds can have a broad range of phosphonium cations and a broad range of phosphinate and dithiophosphinate anions .
  • novel phosphonium phosphinates have the general formula (I) :
  • each of R lf R 2 , R 3 , R 4 , R 5 , and R 6 is independently a hydrogen atom or a hydrocarbyl group, provided that not more than two of R x to R 4 and not more than one of R 5 and R 6 are hydrogen;
  • Y x is O or S
  • Y 2 is 0 or S.
  • each of R x to R 6 is a hydrocarbyl group.
  • the invention provides a process for preparing a phosphonium phosphinate compound of formula (I) , as defined above, wherein:
  • M k+ is H + or a metal cation with valency "k” .
  • X ' is a leaving group other than OH "
  • the reaction is carried out in the presence of a base.
  • a base is not needed if X ⁇ is OH ⁇ and M k+ is H + . If M k+ is a metal cation with valency "k” , then X " is a leaving group other than OH " .
  • R x to R 4 are as defined above for formula (I) and
  • X " is a leaving group, for example hydroxide (OH ⁇ ) , acetate, sulfate, or a halide, preferably chloride, bromide or iodide,
  • R 5; R 6 , Yi and Y 2 are as defined above for formula (I) , and
  • a base for example a hydroxide or a carbonate of an alkali metal or alkaline earth metal.
  • compounds according to formula (I) can also be prepared by reacting a compound of the formula (II) , as defined above, with ii) a compound of the formula (IV) : Formula (IV)
  • R 5 , R 6 , Yi and Y 2 are as defined above for formula (I) , and
  • M is ammonium or a metal and k is the valency of the metal .
  • Appropriate metals are any metals that form water- soluble salts with anions, for example, alkali metals, preferably Na + or K + .
  • the compounds according to formula (I) are useful as ionic solvents.
  • Figure 1 shows the results of a TGA assay on trihexyl (tetradecyl) phosphonium bis (2,4, 4'-trimethyl- pentyl ) phosphinate .
  • Figure 2 shows the results of a TGA assay on trihexyl (tetradecyl) phosphonium diisobutylphosphinate.
  • Figure 3 is a 31 P NMR spectrum of trihexyl (tetradecyl) phosphonium dicyclo-hexylphosphinate.
  • Figure 4 shows the results of a thermogravimetric analysis (TGA) assay on trihexyl (tetradecyl) phosphonium dicyclohexylphosphinate .
  • Figure 5 is a 31 P NMR spectrum of trihexyl- (tetradecyl) phosphonium diisobutyldithiophosphinate.
  • Figure 6 shows the results of a TGA assay on trihexyl (tetradecyl) phosphonium diisobutyldithiophosphinate .
  • the current invention concerns compounds of the general formula (I) , as defined above, wherein: each of Ri, R 2 , R 3 , R 4 , R 5 , and R e is independently a hydrogen or hydrocarbyl group; Yi is O or S; and Y 2 is O or S. It is possible for the groups R x to R s to bear substituents, or to include heteroatoms, provided that the substituents or heteroatoms do not interfere with the preparation of the compounds of the invention, and do not adversely affect the desired properties of the compound. Acceptable substituents include alkoxy, alkylthio, acetyl, and hydroxyl groups, and acceptable heteroatoms include oxygen and sulphur.
  • each of R 1# R 2 , R 3 , R 4 , Rs, and R 6 is independently an alkyl group of 1 to 30 carbon atoms, a cycloalkyl group of 3 to 7 carbon atoms, an alkenyl group of 2 to 30 carbon atoms, an alkynyl group of 2 to 30 carbon atoms, an aryl group of 6 to 18 carbon atoms, or an aralkyl group.
  • Alkyl groups that exceed 18 carbon atoms, especially those that exceed 20 carbon atoms, are likely to increase costs. Since cost is a significant factor in producing a solvent, it is contemplated that, for practical purposes, the alkyl groups will typically not exceed 20 carbon atoms.
  • each of Ri, R 2 , R 3 , R , Rs, and R 6 is independently an alkyl group of 5 to 20 carbon atoms.
  • R 1# R 2/ R 3 , R 4 , R 5 , and R 6 may be n-butyl, isobutyl, n-pentyl, cyclopentyl, isopentyl, n-hexyl, cyclohexyl, (2,4,4'- trimethyl)pentyl, cyclooctyl, tetradecyl, etc., although it is preferred that at least one of Ri to R 4 contains a higher number of carbon atoms, for example 14 or more.
  • Ri to R 4 shall not be identical.
  • at least one of R x to R 4 shall contain a significantly higher number of carbon atoms than the others of Ri to R 4 .
  • Compounds in which R 2 to R 4 are not identical are referred to as asymmetric.
  • Y x and Y 2 are both O.
  • Yi and Y 2 are both 0 because the presence of thio groups in the phosphinate anion may interfere with the action of the catalyst.
  • Phosphonium thiophosphinate compounds find utility as solvents for chemical reactions that do not involve metal catalysts.
  • Preferred compounds include compounds according to formula (I) wherein each of Ri, R 2 , R 3 , R 4 , R 5 , and R 6 , is independently an aryl group or substituted aryl group.
  • R if R 2 , R 3/ R 4/ Rs, and R 6 may be phenyl, phenethyl, xylyl, or naphthyl.
  • compounds according to formula (I) that are hydrophobic or "water immiscible” are preferred.
  • water immiscible is intended to describe compounds that form a two phase system when mixed with water but does not exclude ionic liquids that dissolve in water nor ionic liquids that will dissolve water, provided that the two phase system forms. Therefore, compounds that have a large total number of carbons, equal to or greater than 20 and in particular greater than 25 or 26, or have at least one aryl group are preferred because they are more hydrophobic.
  • Water immiscibility is a desirable feature of phosphonium phosphinates not only because it renders the compounds useful for biphasic reactions with an aqueous phase, but also because it facilitates purification and isolation of the phosphonium phosphinate when prepared according to certain methods.
  • a material that is a liquid at room temperature is very valuable.
  • Preferred compounds are those in which the particular groups Rj . to R 6 are selected to yield compounds that are liquid at room temperature. Selection of particular values for Ri to R 6 to achieve particular melting points and degrees of water immiscibility is within the competence of a person skilled in the art, although it may require some routine experimentation.
  • the degree of asymmetry and branching of the hydrocarbyl groups R ⁇ to R 6 of the phosphonium cation or phosphinate anion are important determinants of the melting point: the melting point tends to decrease as the degree of asymmetry and branching is increased. Branching can occur at the alpha or omega carbon or at any intermediate point .
  • Examples of preferred compound according to formula (I) include those in which:
  • each of R l f R 2 , and R 3 is n-hexyl and R is n- tetradecyl and
  • R 5 and R s are 2 ,4 , 4'-trimethylpentyl and Y x and Y 2 are
  • R 5 and R 6 are isobutyl and Yi and Y 2 are 0; or
  • R 5 and R 6 are cyclohexyl and Yi and Y 2 are 0; or
  • R 5 and R e are isobutyl and Y x and Y 2 are S.
  • the current invention also provides methods for preparing the phosphonium phosphinate compounds according to formula (I) .
  • phosphonium phosphinates can be prepared by reacting a phosphonium salt of formula (II) with either: 1) a phosphinic acid of formula (III) and a base, or 2) a phosphinate salt of formula (IV) .
  • phosphonium phosphinates can be prepared by reacting a phosphonium hydroxide of formula (II) with a phosphinic acid.
  • the temperature of the reaction is not critical, but the reaction is conveniently done at elevated temperature, up to about 100° C, preferably in the range of 45-70° C. Use of a higher temperature facilitates phase separation.
  • a phosphonium phosphinate is immiscible with water, it can be prepared by first mixing a phosphonium salt of formula (II) with a phosphinic acid compound of formula (III) and water, with stirring or other means of mixing, then adding a base. The mixture is stirred for an additional period. When mixing is stopped, the reaction mixture will separate into an organic phase that contains the phosphonium phosphinate product and an aqueous phase. The aqueous phase can be decanted, and the organic phase can then be washed with water to remove the salt byproducts formed by the reaction (for example, sodium chloride) . If desired, residual water can be removed from the organic layer by, for example, vacuum-stripping.
  • the phosphonium salt and water are mixed together first, then sodium hydroxide is added, and the phosphinic acid is added last.
  • the reaction mixture will separate into an aqueous phase and organic phase that can be processed further as described in the method above.
  • Phosphonium phosphinates according to formula (I) that are immiscible with water can also be prepared by mixing a phosphonium salt of formula (II) with a phosphinate salt of formula (IV) and water, with stirring. The mixture is stirred for an additional period, say one hour. When mixing is stopped, the reaction mixture will separate into aqueous and organic layers. The aqueous layer can be decanted, and the organic layer can be washed several times with water, to remove any remaining [M + ] [X " ]*. If desired, dissolved water can be removed from the organic layer by, for example, vacuum- stripping.
  • Phosphonium phosphinates according to formula (I) can be prepared by reacting a phosphonium hydroxide of formula (II), i.e. a compound of formula (II) in which X " is OH " , with a phosphinic acid of formula (III) to produce a phosphonium phosphinate and water.
  • a phosphonium hydroxide of formula (II) i.e. a compound of formula (II) in which X " is OH "
  • a phosphinic acid of formula (III) a phosphinic acid of formula (III)
  • this method can be used to prepare phosphonium phosphinates that are either miscible or immiscible with water. This method is preferred for preparing phosphonium phosphinates that have a small total number of carbons, of the order of 7 to 10 carbons.
  • the compounds of formula (I) contain up to six hydrocarbyl groups Ri to R 6 .
  • the particular properties of a compound of formula (I) depend upon the values taken by these six groups. Selection of different values for these groups therefore permits fine tailoring of the properties of the compound of the invention.
  • compounds can be designed to be liquid at a particular temperature and to be water- immiscible. Change in the value of one or more of the groups Ri to R 6 can effect change in these properties.
  • the presence of six groups for this purpose is advantageous when compared with known ionic liquids based on dialkylimidazolium cations, which have only two groups that can be varied.
  • compounds of the invention have a density less than 1. Consequently, they form the upper phase of two phase systems with water. In this respect, they differ from known ionic liquids based on dialkyl imidazolium cations, which tend to have a density greater than 1 and therefore form the lower phase of two phase systems with water.
  • phosphonium phosphinate salts of the current invention may be used as polar solvents.
  • phosphonium phosphinates of the current invention can be used as polar solvents for chemical reactions such as Michael additions, aryl coupling, Diels-Alder, alkylation, biphasic catalysis, Heck reactions, hydrogenation, or for enzymatic reactions, for example lipase reactions.
  • the phosphonium phosphinates of the current invention are suitable solvents for the synthesis of biphenyl via homo-coupling of bromobenzene or iodobenzene.
  • Biaryls are of great importance in synthetic organic chemistry, as they have found many industrial and pharmacological applications. Elaboration of liquid crystals, for example, often relies on the synthesis of a biaryl framework. Among the natural products biophenomycin and steganacin posses this biaryl molecular substructure. Hence, their production in a cost- effective fashion is especially important.
  • the Ullman Synthesis of biaryls typically demands high temperature conditions (200° C) and requires equimolar amounts of copper.
  • the use of palladium catalysts and an appropriate ionic solvent, such as the phosphonium phosphinates of the current invention, may avoid the need for stoichiometric amounts of metal and high temperature .
  • Example 8 the suitability of the phosphonium phosphinates as solvents for palladium catalyzed carbonylation is demonstrated.
  • the palladium catalyzed carbonylation reactions of aryl-X derivatives constitute a powerful method of C-C coupling reaction for the synthesis of various aromatic carboxylate acid derivatives such as amides and esters.
  • the aryl palladium species formed as the intermediate undergoes the facile CO insertion, followed by the nucleophilic attack of alcohol, water, and amines to give the acid, esters and amides respectively.
  • This reaction can be carried out using aryl halide with carbon monoxide and a nucleophile in the presence of catalytic amount of a palladium compound.
  • Other metal catalysts derived from Co and Ni have also been used as catalysts .
  • yields vary with choice of solvent in the various reactions.
  • the phosphonium phosphinates of the present invention give good, or best, results. Hence they provide a valuable enhancement in methods of synthesis.
  • Trihexyl (tetradecyl) phosphonium bis (2, 4 ,4'-trimethyl- pentyl) phosphinate was prepared according to the following method. A 5 liter stirred jacketed reactor was charged with:
  • the agitation was then turned off and the reaction mixture was allowed to separate into a two-phase system consisting of an upper organic phase and a lower aqueous phase (phase separation took about 2 minutes) .
  • the lower aqueous phase was decanted and the upper organic layer was washed three times with about 1300 g of distilled water per wash, by stirring for one hour at 55° C.
  • the amount of time required for bulk phase separation increased with each successive wash: 2 minutes, 30 minutes, then for the final wash, 8 minutes was required to achieve bulk separation but 22 hours was required for the organic layer to clear.
  • the organic layer was then vacuum stripped to remove dissolved water. Approximately 230 g of water (13.2 % by weight) was removed after vacuum stripping to 125° C under 4 mmHG pressure. The final organic layer was perfectly clear.
  • the aqueous phase was analyzed for chloride ion (see Table 1).
  • the first decant removed 82.9 % of the chloride ion.
  • the first, second, and third washes additionally removed
  • Trihexyl (tetradecyl) phosphonium diisobutylphosphinate was prepared according to the following method. A 5 liter stirred jacketed reactor was charged with:
  • the organic layer was then vacuum stripped to remove dissolved water. Approximately 13.4 % water by weight was removed after vacuum stripping to 135° C under 4 mmHG pressure. The final organic layer was perfectly clear.
  • the decanted aqueous phases were analyzed for chloride ion (see Table 2).
  • the first decant removed 63.7 % of the chloride ion.
  • the first, second, and third washes additionally removed 5.3 %, 0.3 %, and 0.2 % of the chloride ion, respectively, for a total of 69.5 %.
  • Trihexyl (tetradecyl) phosphonium dicyclohexylphosphinate was prepared according to the following method. A stirred jacketed reactor was charged with:
  • the agitation was then turned off and the reaction mixture was allowed to separate into a two-phase system consisting of an upper organic phase and a lower aqueous phase (phase separation took about 4 minutes) .
  • the lower aqueous phase was decanted and the upper organic layer was washed three times by stirring with 1300 g of distilled water.
  • the organic layer was then vacuum stripped to remove dissolved water. Approximately 210 g of water (14 % water by weight) was removed after vacuum stripping to 138° C under 4 mmHG pressure. The final organic layer was perfectly clear.
  • the decanted aqueous phases were analyzed for chloride ion.
  • the first decant removed 82.2 % of the chloride ion, and the first, second, and third washes additionally removed 14.7 %, 1.7 %, and 0.2 % of the chloride ion, respectively, for a total of 98.8 % (see Table 3).
  • Trihexyl (tetradecyl) phosphonium diisobutyl dithiophosphinate was prepared according to the following method. A stirred jacketed reactor was charged with: 1.91 moles of trihexyl (tetradecyl) phosphonium chloride
  • This mixture was heated to 50° C and stirred for 30 minutes. The agitation was then turned off and the reaction mixture was allowed to separate into a two-phase system consisting of an upper organic phase and a lower aqueous phase (phase separation took about 4 minutes) .
  • the lower aqueous phase was decanted and the upper organic layer was washed three times by stirring with 1400 g of distilled water at 50° C.
  • the organic layer was then vacuum stripped to 125° C at 1.2 mmHg pressure. Only 25 g of water was removed. The final organic layer was perfectly clear.
  • the final product was a liquid at room temperature.
  • the chloride content was 0.0099 %.
  • the 31 P NMR spectrum indicated two distinct signals: +33.37 ppm, phosphonium cation; and +65.81 ppm, dithiophosphinate anion ( Figure 5) .
  • Example 5 Biphenyl synthesis via homo-coupling of bromobenzene using Pd(QAc) 2 in various phosphonium ionic liquids
  • R H, alkyl, ether
  • a phosphonium ionic liquid solvent selected from the group consisting of:
  • reaction mixture was allowed to cool, poured into 50 ml water, and the total reaction mixture was extracted with petroleum ether (at 45-60° C) .
  • the ionic liquid formed a middle layer that could be recovered.
  • the petroleum ether layer was washed with water, then with brine, and then concentrated. The residue was distilled to obtain the required biaryl compound.
  • Example 6 Biphenyl synthesis via homo-coupling of iodobenzene in various ionic liquids using Pd(OAc) 2 as catalyst
  • a phosphonium ionic liquid solvent selected from the group consisting of:
  • trihexyl (tetradecyl) phosphonium chloride trihexyl (tetradecyl) phosphonium triflate
  • Example 7 Heck coupling of iodobenzene and methylacrylate in various ionic liquids using Pd(OAc) 2 catalyst
  • the reaction mixture was heated at 80° C for 14 hours in 2.0 g of a phosphonium ionic liquid solvent selected from the group consisting of:
  • Example 8 Carbonylation of iodobenzene in various ionic liquids using Pd(OAc) catalyst
  • the phosphonium ionic liquid solvent selected from the group consisting of:
  • Example 9 Bipyridine synthesis via the homo-coupling of bromopyridine in various ionic liquids using Pd(OAc) 2 catalyst

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PCT/US2002/006104 2001-03-30 2002-02-28 Phosphonium phosphinate compounds and their preparation WO2002079212A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US10/473,271 US20040106823A1 (en) 2001-03-30 2002-02-28 Novel phosphonium phosphinate compounds and their methods of preparation
EP02707923A EP1373280A1 (en) 2001-03-30 2002-02-28 Phosphonium phosphinate compounds and their preparation
BR0208199-7A BR0208199A (pt) 2001-03-30 2002-02-28 Composto, método para preparar um composto de fosfinato de fosfÈnio, e, uso do composto
KR10-2003-7012520A KR20030093282A (ko) 2001-03-30 2002-02-28 포스포늄 포스피네이트 화합물 및 이의 제법

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CA2,343,456 2001-03-30
CA002343456A CA2343456A1 (en) 2001-03-30 2001-03-30 Novel phosphonium phosphinate compounds and their methods of preparation

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KR (1) KR20030093282A (ru)
CN (1) CN1297560C (ru)
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CA (1) CA2343456A1 (ru)
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WO2004094438A1 (en) * 2003-03-31 2004-11-04 Cytec Canada Inc. Phosphonium salts and methods of their preparation
WO2005021484A3 (de) * 2003-08-27 2005-05-26 Roland Kalb Verfahren zur herstellung ionischer flüssigkeiten, ionischer feststoffe oder gemische derselben
GB2433069A (en) * 2005-12-06 2007-06-13 Ngimat Co Ionic liquids comprising carboxylate anions and their preparation using a cationic support resin
WO2008075016A1 (en) * 2006-12-19 2008-06-26 Castrol Limited Lubricating oil compositions and uses
US7886577B2 (en) * 2006-03-30 2011-02-15 Oakland University Devices with surface bound ionic liquids and method of use thereof
US8375768B2 (en) 2006-03-30 2013-02-19 Oakland University Ionic liquid thin layer sensor for electrochemical and/or piezoelectric measurements
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CN108767314A (zh) * 2018-04-16 2018-11-06 兰州大学 一种阻燃离子液体的制备及应用方法

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Cited By (19)

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Publication number Priority date Publication date Assignee Title
WO2004016631A1 (en) * 2002-08-16 2004-02-26 Cytec Canada Inc. Phosphonium and imidazolium salts and methods of their preparation
US7638636B2 (en) 2002-08-16 2009-12-29 Cytec Technology Corp. Phosphonium and imidazolium salts and methods of their preparation
KR101074256B1 (ko) 2003-03-31 2011-10-14 사이텍 캐나다 인코포레이티드 포스포늄 염과 그 제조 방법
WO2004094438A1 (en) * 2003-03-31 2004-11-04 Cytec Canada Inc. Phosphonium salts and methods of their preparation
US8748668B2 (en) * 2003-03-31 2014-06-10 Cytec Technology Corp. Phosphonium salts and methods of their preparation
US20110021838A1 (en) * 2003-03-31 2011-01-27 Cytec Canada Inc. Phosphonium salts and methods of their preparation
WO2005021484A3 (de) * 2003-08-27 2005-05-26 Roland Kalb Verfahren zur herstellung ionischer flüssigkeiten, ionischer feststoffe oder gemische derselben
US8075803B2 (en) 2003-08-27 2011-12-13 Roland Kalb Method for producing ionic liquids, ionic solids or mixtures thereof
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CA2343456A1 (en) 2002-09-30
EP1373280A1 (en) 2004-01-02
KR20030093282A (ko) 2003-12-06
CN1529708A (zh) 2004-09-15
BR0208199A (pt) 2004-03-02
CN1297560C (zh) 2007-01-31

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