WO2005019185A1 - Ionic liquids based on imidazolium salts incorporating a nitrile functionality - Google Patents

Ionic liquids based on imidazolium salts incorporating a nitrile functionality Download PDF

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WO2005019185A1
WO2005019185A1 PCT/EP2004/009499 EP2004009499W WO2005019185A1 WO 2005019185 A1 WO2005019185 A1 WO 2005019185A1 EP 2004009499 W EP2004009499 W EP 2004009499W WO 2005019185 A1 WO2005019185 A1 WO 2005019185A1
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nmr
ionic liquids
synthesis
alkyl
cnf
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Paul Dyson
Dongbin Zhao
Zhaofu Fei
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Ecole Polytechnique Federale de Lausanne EPFL
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Ecole Polytechnique Federale de Lausanne EPFL
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Priority to EP04764475A priority Critical patent/EP1660457B1/en
Priority to AU2004266847A priority patent/AU2004266847B2/en
Priority to MXPA06002214A priority patent/MXPA06002214A/en
Priority to BRPI0414005-2A priority patent/BRPI0414005A/en
Priority to US12/087,749 priority patent/US8101777B2/en
Priority to ES04764475T priority patent/ES2374195T3/en
Priority to PL04764475T priority patent/PL1660457T3/en
Priority to CN2004800238207A priority patent/CN1839122B/en
Application filed by Ecole Polytechnique Federale de Lausanne EPFL filed Critical Ecole Polytechnique Federale de Lausanne EPFL
Priority to AT04764475T priority patent/ATE526314T1/en
Priority to CA002534864A priority patent/CA2534864A1/en
Priority to JP2006524325A priority patent/JP4791361B2/en
Publication of WO2005019185A1 publication Critical patent/WO2005019185A1/en
Anticipated expiration legal-status Critical
Priority to US13/328,353 priority patent/US20120108820A1/en
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    • C07D233/56—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 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
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Definitions

  • This invention relates to novel ionic liquids.
  • the ionic liquids can be used as solvents to immobilize catalysts for the biphasic or multiphasic synthesis of chemical products such as pharmaceuticals.
  • Ionic liquids are salts with a melting temperature below the boiling point of water. Ionic liquids useful as solvents in industrial applications are also liquids at room temperature.
  • ionic liquids are also finding uses in separation processes, in electrochemistry, as electrolytes in solar cells, as lubricants, and as matrices in MALDI mass spectrometry.
  • One of the attractive features of ionic liquids in synthesis and catalysis is that both the cationic and anionic components can be varied and modified, so that a liquid can be tailored to specific applications.
  • task-specific ionic liquids has been used to describe low melting salts with functional groups, such as amine and amide, sulfonic acid, ether and alcohol, carboxylic, urea and thiourea and phosphine functionalities, as well as fluorous chains attached to the alkyl side chains.
  • the definition of task-specific ionic liquids is also extended to include ionic liquids with functional anions such as carboranes, metal carbonyl anions such as [Co(CO) 4 ] ⁇ ; the proprietary catalyst [Rh(CO) 2 l 2 r and alkylselenites.
  • ionic liquids are to be used to immobilize catalysts in multiphasic reactions, then the design and synthesis of task-specific ionic liquids is extremely important. Many different reactions have been catalyzed using ionic liquids as immobilization solvents including hydrogenation, hydroformylation and C-C coupling reactions. While the non- nucleophilic nature of many ionic liquids seems to be advantageous, providing a protective environment for the catalyst which can extend its lifetime, it has also emerged that ionic liquids that incorporate a coordination centre might be extremely useful, such that the ionic liquid serves as both immobilization solvent and ligand to the catalyst.
  • the nitrile group is chosen as it is a promising donor to main group metals such as lithium and potassium, as well as lanthanide and actinide series and transition metals such as palladium and platinum.
  • main group metals such as lithium and potassium
  • lanthanide and actinide series and transition metals such as palladium and platinum.
  • Yet another object of this invention is to produce ionic liquids, which provide coordination centers (i.e. that act as ligands), while maintaining a low melting point, less than about 100°C, ideally at or below room temperature (i.e., acting as a solvent).
  • a still further object of the invention is to demonstrate the applicability of these new ionic liquids in catalysis; as they have particular value in the immobilization of catalysts, enabling the catalyst to be recovered and efficiently recycled.
  • K + is a 5- or 6- membered heterocyclic ring having 1-3 hetero atoms, which can be independently N, S, or 0; with the proviso that at least one of the hetero atoms must be a quatemized nitrogen atom having a -R'CN substituent, wherein R' is alkyl (Ci to C 12 ); the heterocyclic ring having up to 4 or 5 substituents independently chosen from the moieties: ( H; (ii) halogen or (iii) alkyl (Ci to C ⁇ 2 ), which is unsubstituted or partially or fully substituted by further groups, preferably F, CI, N(C n F (2n+ ⁇ - x )H x ) 2 , O(C n F (2 possibly +1 .
  • a " is any anion that provides a salt with a low melting point, below about 100° C.
  • A is halide, such as chloride, bromide, fluoride and the like; BF 4 " , PF 6 “ , NO 3 “ , CH3CO 2 “ , CF3SO3 “ , (CF 3 SO 2 ) 2 N-, (CF 3 SO 2 ) 3 C-, CF3CO2 " or N(CN) 2 -.
  • catalysts especially lanthanide and actinide series and transition metal chlorides, such as palladium and platinum chlorides, to form complexes soluble in the ionic liquid.
  • the catalysts can be recovered and recycled easily from the ionic liquids.
  • R'C ⁇ N where R' is an alkyl acts as the functional group and must always be present. More than one R'C ⁇ N group may also be included, either attached to nitrogen or a carbon in the ring.
  • K+ ring particularly preferred as the K+ ring are the pyrrolium, pyrazolium, pyridinium, pyrazinium, pyrimidinium, imidazolium, thiazolium, oxazolium, and triazolium rings, some of which are illustrated in the series depicted below,
  • imidazolium and pyridinium rings are particularly preferred. Essentially any combination of cation with one or more R'C ⁇ N groups with any anion that results in a salt with a melting point below 100°C is included.
  • the invention provides ionic liquids with a functionalized anion, in place of the usual anions which include BF “ , PF 6 " , NO 3 “ , CH 3 CO 2 " , CF 3 SO 3 “ , (CF 3 SO 2 ) 2 N “ , (CF 3 SO 2 ) 3 C “ , CF3CO 2 " , N(CN) 2 * .
  • the functionalized anion may be a nitrile functionalized anion, e.g. [BF 3 RCN] ' wherein R' is alkyl (Ci to C 18 ,for example C 1 to C 12 ).
  • the anion is [BF 3 CHCH 3 CH 2 CN] ' .
  • the synthetic route to prepare the K + A " salts utilizes as starting material the appropriate alkyl-substituted heterocyclic compound, which is then reacted with the appropriate chloroalkyl nitrile.
  • the reactants are employed in approximately equimolar quantities, in a solvent which can be any of the usual solvent systems for heterocyclic chemistry, such as tetrahydofuran, acetonitrile, and diethyl ether.
  • the reaction proceeds at ambient temperatures up to about 200°C.
  • the 1-alkylnitrile-2,3-dimethylimidazolium salt [1-alkylnitrile-3- methylimidazoliumjCI 5a is prepared similarly from 1,2-dimethylimidazole and CI(CH 2 )3CN.
  • the synthesis of 1a has been described previously using an alternative a somewhat more complicated method. Both methods are found in the references: (a) Hitchcock, P. B.; Seddon, K. R.; Welton, T. J. Chem. Soc. Dalton Trans. 1993, 2639. (b) Suarez, P. A. Z.; Dullius, J. E. L; Einloft, S.; de Souza, R. F.; Dupont, J.
  • the imidazolium salts [1-alkylnitrile-3-methylimidazolium]PF 6 5b and [1-alkylnitrile-3- methylimidazolium]BF 4 5c are prepared from 5a using an analogous method.
  • the salts are washed with water in order to remove the hydrogen chloride formed during the anion exchange reaction, whereas tetrohydrofuran and diethyl ether are used to wash 1c - 5c.
  • the salts are then dried under vacuum for 1 - 2 days.
  • the salts 2c, 3c, 4a, 4b and 3c are liquid at room temperature and are further purified by filtration through silica and left under vacuum at 40 - 50°C for several days. All the imidazolium salts are obtained in medium to high yield. They are stable in air and show no signs of decomposition up to 150°C.
  • the synthetic route to prepare ionic liquids with a functionalized anion involves the preparation of the anion as a potassium salt, followed by anion metathesis with various imidazolium halides.
  • the synthesis of e.g. K[BF 3 CHCH 3 CH 2 CN] " is depicted in Scheme 2.
  • the first step of the anion synthesis involves hydroboration of allyl cyanide using boron trichloride and triethylsilane, then addition of water to afford the boronic acid wich is subsequently stirred with KHF 2 in ether/H 2 O at ambient temperature.
  • ionic liquids can react with lanthanide and actinide series and transition metal chlorides and other metal salts or compounds used as catalysts to form complexes, for example, with PdCI 2 , PtCI 2 , RuCI 3 , RhCI 3 , and [Ru(arene)CI 2 ] 2 - Included within the term salts are not only the chlorides, but other salts which are known and employed to those skilled in the art.
  • Metal containing molecular compounds used as catalysts e.g. Wilkinson's catalyst and Grubb's catalyst, or the like can also be employed in this invention.
  • the process of making the complex is a straightforward one of dissolving a catalytically effective amount of the desired catalyst in enough of the ionic liquid to form a solution. If the catalyst and ionic liquid solution is to be used immediately in a catalyzed reaction, the amounts of the two can be those required for the reaction, the ionic liquid serving as solvent for the reaction step immediately following.
  • the reaction product usually is separated from the reactants by solvent extraction, but the immobilized catalyst remains in the ionic liquid solvent, so is recovered and can be used for another reaction.
  • the catalyst can also be prepared in a concentrated form in the ionic liquid , then later diluted with an excess of the ionic liquid to the desired catalyst concentration.
  • the main advantages of the invention are: 1.
  • the ionic liquids act as both ligand and solvent when used as media for organic synthesis in multiphasic catalysis, therefore, no other ligands are necessary.
  • the catalysts are strongly immobilized in the ionic liquids and can be easily recycled without loss (or minimal loss) of the catalyst.
  • the dual-functionalized ionic liquids are particularly advantageous due to their very low viscosities, e.g. as shown in Examples 33 to 35.
  • the nitrile derivatized ionic liquids of this invention are useful as solvents for multiphasic catalysis, in terms of catalyst retention and product separation. Dissolution of PdCI 2 in [C 3 CNmim][BF 4 ] 3c affords [Pd(NCC 3 mim) 2 CI 2 ][BF 4 ] 2 in quantitative yield. The resulting solution is used to hydrogenate 1 ,3,-cyclohexadiene under biphasic conditions, which affords cyclohexene and cyclohexane.
  • the overall conversion is 90% and the turnover frequency 247 molmol "1 h "1 ; cyclohexene is formed with a selectivity of 97%. This is possibly because the monoene dissociates from the catalyst and is less soluble in the ionic liquid than the diene, which is therefore hydrogenated in preference. Hydrogenation reactions have been widely studied in ionic liquids, including the substrate 1 ,3-cyclohexadiene, but this would appear to be the first time selectivity to cyclohexene has been observed. Selective hydrogenation of 1,3- cyclohexadiene using palladium and platinum complexes with chiral ferrocenylamine sulfide and selenide ligands has been reported previously.
  • the palladium ionic liquids system gives such selectivity without the need for aditional co- ligands.
  • the most important feature of this system is that the catalyst is part of the ionic liquid and therefore not easily lost during extraction of the product. No decrease in activity is observed after re-use of the catalyst solution. No palladium residues in the organic phase are detected using inductively coupled plasma analysis.
  • the 1-methylimidazole and 1 ,2-dimethylimidazole and chloronitriles are purchased from Fluka, HPF 6 and NaBF are purchased from Aldrich and are used as received without further purification.
  • the synthesis of the imidazolium salts 1a - 5a is performed under an inert atmosphere of dry nitrogen using standard Schlenk techniques in solvents dried using the appropriate reagents and distilled prior to use. All other compounds are made without precautions to exclude air or moisture.
  • IR spectra are recorded on a Perkin-Elmer FT-IR 2000 system. NMR spectra are measured on a Bruker DMX 400, using SiMe 4 for 1 H, 85% H 3 PO 4 for 31 P, as external standards at 20°C.
  • Electrospray ionization mass spectra are recorded on a ThermoFinnigan LCQTM Deca XP Plus quadrupole ion trap instrument on sample diluted in methanol. 19 Samples are infused directly into the source at 5 ⁇ L min "1 using a syringe pump and the spray voltage is set at 5 kV and the capillary temperature at 50°C. Samples 2c, 3c, 4a, 4b and 4c are purified by filtration through silica and left under vacuum (ca. 0.1 mm Hg) at 40 - 50°C in order to remove traces of salt impurities and volatile components. Differential scanning calorimetry is performed with a SETARAM DSC 131.
  • Density is determined with a picometer at room temperature (20 ⁇ 1 °C) on 1.0 ml of sample. The measurements are repeated three times and average values are used. Viscosities are measured with a Brookfield DV-II+ viscometer on 0.50 ml of sample. The temperature of the samples is maintained to 25 ⁇ 1°C by means of an external temperature controller. The measurements are performed in duplicate.
  • EXAMPLE 1 Synthesis o/ " 1-methylnitrile-3-methylimidazolium7C7 1a
  • a mixture of 1-methylimidazole (8.21 g, 0.10 mol) and CICH 2 CN (9.06 g, 0.12 mol) is stirred at room temperature for 24 hours, during which time the reaction mixture turned to a solid.
  • the solid is washed with diethyl ether (3 x 30 ml) and dried under vacuum for 24 hours, yield: 14.5 g, 92%; M.p. 170°C. Crystals suitable for X-ray diffraction are obtained by slow diffusion of ethyl ether into an acetonitrile solution of the compound at room temperature.
  • EXAMPLE 4 Synthesis o71-ethylnitrile-3-methylimidazoliu ⁇ /C/ 2a
  • a mixture of 1-methylimidazole (8.21g, 0.10 mmol) and CI(CH 2 ) 2 CN (10.74 g, 0.12 mol) is stirred in toluene (20 ml) at 70°C for 24 hours.
  • the resulting white solid is washed with diethyl ether (5 x 30 ml).
  • the product is then dried in vacuum for 24 hours. Yield: 15.5g, 82%; M.p. 50°C.
  • ESI-MS (CH 3 OH): Positive ion: 136 [C 2 CNmim], negative ion: 35 [CI].
  • EXAMPLE 6 Synthesis of 1-ethylnitrile-3-methylimidazoliurn/SF 4 2c The same procedure is followed as that described above for 1c, except 2a (5.15 g, 0.03 mol) is used instead of 1a. The product is obtained as pale yellow liquid at room temperature. Yield: 5.69 g, 85%; M.p. 20°C.
  • ESI-MS (CH 3 OH): Positive ion: 136 [C 2 CNmim], negative ion: 87 [BF 4 ].
  • EXAMPLE 7 Synthesis of/l-propylnitrile-3-methylimidazoliurn/C/ 3a
  • a mixture of 1-methylimidazole (8.21g, 0.10 mmol) and CI(CH 2 ) 3 CN (12.43g, 0.12 mol) is stirred at 80°C for 24 hours.
  • the resulting white solid is washed with diethyl ether (3 * 30 ml).
  • the product is dried in vacuum for 24 hours. Yield: 17.6 g, 95%; M.p. 80°C.
  • ESI-MS (CH 3 OH): Positive ion: 150 [C 3 CNmim], negative ion: 35 [CI].
  • EXAMPLE 8 Synthesis of " 1-propylnitrile-3-methylimidazolium;PF 6 3b The same procedure is followed as that described above for 1b, except 3a (5.57 g, 0.03 mol) is used instead of 1a. The product is obtained as white solid. Yield: 6.90 g, 78%; M.p. 75°C. ESI-MS (CH 3 OH): Positive ion: 150 [C 3 CNmim], negative ion: 145 [PF 6 ].
  • EXAMPLE 9 Synthesis of [1-propylnitrile-3-methylimidazoliurn/SF 4 3c The same procedure is followed as that described above for 1c, except 3a (5.57 g, 0.03 mol) is used instead of 1a. Yield: 6.4 g, 90%; M. p. -71.9°C.
  • EXAMPLE 10 Synthesis of / ' 1-butylnitrile-3-methylirnidazoliurn/C/ 4a
  • a mixture of 1-methylimidazole (8.21g, 0.10 mmol) and CI(CH 2 ) 4 CN (14.1g, 0.12 mol) is stirred at 80°C for 4 hours. The temperature is then increased to 110°C and the reaction mixture is stirred at for further 2 hours. After cooling, the reaction mixture is washed with diethyl ether (3 *15 ml) and dried under vacuum for 24 hours. The product is obtained as viscous brownish liquid. Yield: 17.9 g, 90%; M.p. 32°C.
  • EXAMPLE 11 Synthesis o/71-butylnitrile-3-methylimidazoliurn/PF 6 4b The same procedure is followed as that described above for 1b, except 4a (5.99 g, 0.03 mol) is used instead of 1a. The product is obtained as brown liquid at room temperature. Yield: 7.6 g, 82%; M.p. -60.3°C. ESI-MS (CH 3 OH): positive ion: 164 [C 3 CNmim], negative ion: 145 [PF 6 ].
  • EXAMPLE 13 Synthesis of / ' 1-methylnitrile-2,3-dimethylimidazolium7C/ 5a
  • a mixture of 1 ,2-dimethylimidazole (9.61 g, 0.10 mol) and CI(CH 2 ) 3 CN (12.43 g, 0.12 mol) is stirred at 100°C for 24 hours.
  • Two phases are formed at the end of the reaction. The upper phase is decanted and the lower phase is washed with diethyl ether (3 * 30 ml). A pale yellow solid is formed during the washing and the product is dried in vacuum for 24 hours at room temperature. Yield: 18.6 g, 93%; M.p. 105°C.
  • EXAMPLE 14 Synthesis of 1-methylnitrile-2,3-dimethylimidazolium;PF 6 5b The same procedure is followed as that described above for 1b, except 5a (5.99 g, 0.03 mol) is used instead of 1a. The product is obtained as white solid at room temperature. Yield: 7.33 g, 79%; M.p. 85°C. ESI-MS (CH 3 OH): Positive ion: 164 [C 3 CNdimim], negative ion: 145 [PF 6 ].
  • EXAMPLE 15 Synthesis of /1-methylnitrile-2,3-dimethylimidazolium;BF 4 5c The same procedure is followed as that described above for 1c, except 5a (5.99 g, 0.03 mol) is used instead of 1a. The product is obtained as white waxy solid at room temperature. Yield: 6.77 g, 90%; M.p. 40°C. ESI-MS (CH 3 OH): Positive ion: 164 [C 3 CNdimim], negative ion: 87 [BF 4 ].
  • EXAMPLE 16 Synthesis of / ⁇ Po , 1-methylnitrile-2,3-dimethylimidazoliumJ 2 C/27/ ' ⁇ F 2 A mixture of 5c (153 mg, 0.61 mmol) and palladium chloride (54 mg, 0.305 mmol) in 5.0 ml dichloromethane is stirred at room temperature for 3 days. The resulting yellow solid is extracted by filtration, washed with diethyl ether (2 x 5.0 ml) and dried in vacuum.
  • EXAMPLE 17 Synthesis of[1-cyanopropyl-3-methylimidazolum] 2 [PdCI 4 ]
  • a reaction mixture of PdCI 2 (177 mg, 1.0 mmol) and 3a (377 mg, 2.00 mmol) in dichloromethane (2 ml) is stirred at r.t. for 4 days.
  • the resulting orange solid is collected by centrifugation and washed with dichloromethane (20 ml). Drying in vacuum gave the product in pure form. Yield: 548 mg, 100%. Mp: 178°C.
  • EXAMPLE 19 Hydrogenation of 1 ,3-cyclohexadiene by PdCI 2 in 3c PdCI 2 ( ⁇ 5 mg) is dissolved in ionic liquid 3c (1 ml), and 1 ,3-cyclohexadiene (1 ml) is added. The reaction is pressurized with H 2 to 45 atm, sealed and heated to 100°C for 4 h which gave cyclohexene in 90% yield. The product is simply removed by decantation and no palladium is detected (based on ICP analysis).
  • Complexes 7a, 7b, 7c are used for Suzuki coupling reaction of iodobenzene and benzeneboronic acid, as shown in scheme 2, above, lodobenzene (2.5 mmol, 1 equiv.), benzenboronic acid (2.75 mmol, 1.1 equiv.), Na 2 CO 3 (560 mg, 5.28 mmol, 2.1 equiv.), palladium complex (0.03 mmol) and water (2.5 ml) are mixed with [C 4 mim][BF 4 ] (5 ml). The mixture is heated to 110°C with vigorous stirring for 12 hours, then cooled and extracted with diethyl ether (3 * 15 ml). The combined organic phase is dried over MgSO 4 and filtered.

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Abstract

Novel chemical compounds of the general formula K+A-, in which K+ is a 5- or 6- membered heterocyclic ring having 1-3 hetereo atoms, which can be independently N, S, or 0; with the proviso that at least one of the hetereo atoms must be a quaternized nitrogen atom having a -R'CN substituent, wherein R' is alkyl (C1 to C12); the heterocyclic ring having up to 4 or 5 substituents independently chosen from the moieties: (i) H; (ii) halogen or (iii) alkyl (C1 to C12) , which is unsubstituted or partially or fully substituted by further groups, preferably F, Cl, N(CnF(2n+1-x)Hx)2, O(CnF(2n+1-x)Hx), S02(CnF(2n+1-x)Hx)2 or CnF(2n+1-x)Hx where 1<n<6 and 0<x<13; and (iv) a phenyl ring which is unsubstituted or partially or fully substituted by further groups, preferably F, Cl, N(CnF(2n+1-x.)Hx.)2, O(CnF(2n+1-x)Hx), S02(CnF(2n+1-x)Hx)2 or CnF(2n+1-x)Hx where 1<n<6 and 0<x≤13; and A- is any anion that provides a salt with a low melting point, below about 100 °C; A- can be halide, BF4- , PF6-, N03-, CH3CO2-, CF3SO3-, (CF3SO2)2N-, (CF3SO2)3C- CF3CO2- or N(CN)2- or [BF3RCN]-. These compounds can be used as industrial solvents, especially as ligands for efficient catalyst recycling.

Description

IONIC LIQUIDS BASED ON IMIDAZOLIUM SALTS INCORPORATING A NITRILE FUNCTIONALITY
Field of the Invention This invention relates to novel ionic liquids. The ionic liquids can be used as solvents to immobilize catalysts for the biphasic or multiphasic synthesis of chemical products such as pharmaceuticals.
Background of the Invention Ionic liquids are salts with a melting temperature below the boiling point of water. Ionic liquids useful as solvents in industrial applications are also liquids at room temperature.
Room temperature ionic liquids or molten salts were described for the first time in U. S. Pat. No. 2,446,331. The problem with these ionic liquids described in this patent is that the anionic component can decompose on contact with atmospheric moisture.
More recently, air and moisture stable ionic liquids have been prepared, and now extensive studies have been carried out in two main areas: 1. The development of new ionic liquids based on many different cation and anion combinations. 2. The application of ionic liquids as immobilizing media for lanthanide and actinide series and transition metal catalysts.
Ionic liquids are currently attracting considerable attention as novel solvents for organic synthesis and catalysis because the chemical industry is under pressure to replace environmentally damaging volatile organic solvents with more benign alternatives. "Room temperature ionic liquids", especially those based on 1 ,3- dialkylimidazolium cations, have emerged as leading contenders since they have negligible vapor pressure, are air and moisture stable, and are highly solvating for both ionic and molecular species, and as a result are suitable for multiphasic catalysis. Although applications in synthesis and catalysis have been most widely explored, with the first industrial scale process now on-line for over a year, ionic liquids are also finding uses in separation processes, in electrochemistry, as electrolytes in solar cells, as lubricants, and as matrices in MALDI mass spectrometry. One of the attractive features of ionic liquids in synthesis and catalysis is that both the cationic and anionic components can be varied and modified, so that a liquid can be tailored to specific applications. The term "task-specific ionic liquids" has been used to describe low melting salts with functional groups, such as amine and amide, sulfonic acid, ether and alcohol, carboxylic, urea and thiourea and phosphine functionalities, as well as fluorous chains attached to the alkyl side chains. The definition of task-specific ionic liquids is also extended to include ionic liquids with functional anions such as carboranes, metal carbonyl anions such as [Co(CO)4]~ ; the proprietary catalyst [Rh(CO)2l2r and alkylselenites.
If ionic liquids are to be used to immobilize catalysts in multiphasic reactions, then the design and synthesis of task-specific ionic liquids is extremely important. Many different reactions have been catalyzed using ionic liquids as immobilization solvents including hydrogenation, hydroformylation and C-C coupling reactions. While the non- nucleophilic nature of many ionic liquids seems to be advantageous, providing a protective environment for the catalyst which can extend its lifetime, it has also emerged that ionic liquids that incorporate a coordination centre might be extremely useful, such that the ionic liquid serves as both immobilization solvent and ligand to the catalyst. Wasserscheid et al first described this concept by introducing a diphenylphosphine group at the 2-position of an imidazolium cation; the resulting salt was a not a "room temperature ionic liquid" and had to be dissolved in another ionic liquid for effective use in biphasic catalysis. The ligand, by virtue of being a salt, is highly soluble in ionic liquids and is strongly retained during product extraction. Groups such as NH2 and OH have also been successfully introduced into the imidazolium cation moieties but their ability to coordinate to lanthanide and actinide series and transition metals to give catalytically useful complexes is somewhat limited. More sophisticated functional groups such as thioureas and thioethers have been tethered to imidazolium based ionic liquids and they have been shown to extract toxic metal ions from aqueous solution.
It is one object of this invention to provide the synthesis and characterization of quatemized nitrogen-containing heterocyclic compounds, e.g. especially imidazolium or pyridinium heterocyclic compounds, such as salts, in which a nitrile group is attached to the alkyl side chain. The nitrile group is chosen as it is a promising donor to main group metals such as lithium and potassium, as well as lanthanide and actinide series and transition metals such as palladium and platinum. The physicochemical properties of these new ionic liquids are described. It is a further object of this invention to provide information about the relationship of the length of the alkyl unit linking the quatemized nitrogen-containing heterocyclic ring and the CN group, and how this relationship influences the melting point of the ionic liquid. Yet another object of this invention is to produce ionic liquids, which provide coordination centers (i.e. that act as ligands), while maintaining a low melting point, less than about 100°C, ideally at or below room temperature (i.e., acting as a solvent). A still further object of the invention is to demonstrate the applicability of these new ionic liquids in catalysis; as they have particular value in the immobilization of catalysts, enabling the catalyst to be recovered and efficiently recycled.
It is yet a further aspect of the invention to provide dual-functionalized ionic liquids and their properties.
Description and Summary of the Invention
Novel chemical compounds are provided of the general formula,
K+A-,
in which K+ is a 5- or 6- membered heterocyclic ring having 1-3 hetero atoms, which can be independently N, S, or 0; with the proviso that at least one of the hetero atoms must be a quatemized nitrogen atom having a -R'CN substituent, wherein R' is alkyl (Ci to C12); the heterocyclic ring having up to 4 or 5 substituents independently chosen from the moieties: ( H; (ii) halogen or (iii) alkyl (Ci to Cι2), which is unsubstituted or partially or fully substituted by further groups, preferably F, CI, N(CnF(2n+ι-x)Hx)2, O(CnF(2„+1.x)Hx), SO2(C„F(2n+ι*)Hx)2 or CnF(2n+ι-x)Hx where 1<n<6 and 0<x<13; and (iv) a phenyl ring which is unsubstituted or partially or fully substituted by further groups, preferably F, CI, N(CnF(2n+ι-X)Hχ)2, O(CnF(2n+i-x)Hx), SO2(CnF(2n+ι.x)Hx)2 or CnF(2n+i-x)Hx where 1 <n<6 and 0<x<13; and A" is any anion that provides a salt with a low melting point, below about 100° C. Most preferably, A is halide, such as chloride, bromide, fluoride and the like; BF4 ", PF6 ", NO3 ", CH3CO2 " , CF3SO3", (CF3SO2)2N-, (CF3SO2)3C-, CF3CO2" or N(CN)2-.
These compounds are useful in the immobilization of catalyst, especially lanthanide and actinide series and transition metal chlorides, such as palladium and platinum chlorides, to form complexes soluble in the ionic liquid. The catalysts can be recovered and recycled easily from the ionic liquids.
In the above compounds, the group R'C≡N where R' is an alkyl acts as the functional group and must always be present. More than one R'C≡N group may also be included, either attached to nitrogen or a carbon in the ring.
Particularly preferred as the K+ ring are the pyrrolium, pyrazolium, pyridinium, pyrazinium, pyrimidinium, imidazolium, thiazolium, oxazolium, and triazolium rings, some of which are illustrated in the series depicted below,
Figure imgf000005_0001
Most particularly preferred are the imidazolium and pyridinium rings. Essentially any combination of cation with one or more R'C≡N groups with any anion that results in a salt with a melting point below 100°C is included.
In a further aspect the invention provides ionic liquids with a functionalized anion, in place of the usual anions which include BF ", PF6 ", NO3 ", CH3CO2 " , CF3SO3 ", (CF3SO2)2N", (CF3SO2)3C", CF3CO2 ", N(CN)2 *. The functionalized anion may be a nitrile functionalized anion, e.g. [BF3RCN]' wherein R' is alkyl (Ci to C18,for example C1 to C12). Preferably the anion is [BF3CHCH3CH2CN]'.
HOW TO MAKE THE IONIC K*A LIQUIDS
The synthetic route to prepare the K+A" salts utilizes as starting material the appropriate alkyl-substituted heterocyclic compound, which is then reacted with the appropriate chloroalkyl nitrile. The reactants are employed in approximately equimolar quantities, in a solvent which can be any of the usual solvent systems for heterocyclic chemistry, such as tetrahydofuran, acetonitrile, and diethyl ether. The reaction proceeds at ambient temperatures up to about 200°C.
The synthesis of e.g., 1-alkylnitrile-3-methylimidazolium and 1 -alkylnitrile-2,3- dimethylimidazolium salts is depicted in Scheme 1 , below. The imidazolium chlorides, e.g., [1-alkylnitrile-3-methylimidazolium][CI] , wherein alkyl is C=1-12, especially C=1-4, such as (Cn = (CH )n> n = 1 1a, n = 22a, n = 3 3a and n = 44a) are prepared in high yield from 1-methylimidazole and the appropriate chloroalkyl nitrile CI(CH2)nCN in a modification to the literature procedure for the related 1-aIkyl-3-methylimidazolium chlorides. The 1-alkylnitrile-2,3-dimethylimidazolium salt [1-alkylnitrile-3- methylimidazoliumjCI 5a is prepared similarly from 1,2-dimethylimidazole and CI(CH2)3CN. The synthesis of 1a has been described previously using an alternative a somewhat more complicated method. Both methods are found in the references: (a) Hitchcock, P. B.; Seddon, K. R.; Welton, T. J. Chem. Soc. Dalton Trans. 1993, 2639. (b) Suarez, P. A. Z.; Dullius, J. E. L; Einloft, S.; de Souza, R. F.; Dupont, J. Polyhedron 1996, 15, 1217, and Herrmann, W. A.; Goossen, L. J.; Spiegler, M.; Organometallics 1998, 17, 2162. The relatively strong electron withdrawing effect of the nitrile group activates chloromethylacetonitrile CICH2CN to such an extent that it reacts smoothly with 1- methylimidazole in the absence of solvent to give 1a. However, as the alkyl chain in the chloroalkyl nitrile CI(CH2)nCN precursor increases in length, the temperature required to complete the reaction also increases.
Scheme 1
Figure imgf000007_0001
1a - 5a HPF6 or NaBF„
Figure imgf000007_0002
1b/c - 5b/c
Scheme 1 : Synthesis of ionic liquids: 1a n = 1 , R = H; 2a n = 2, R = H; 3a n = 3, R = H; 4a n = 4, R = H; 5a n = 3, R = CH3; 1b n = 1 , R = H, A = PF6; 1c n = 1 , R = H, A = BF4; 2b n = 2, R = H, A = PF6; 2c n = 2, R = H, A = BF4; 3b n = 3, R = H, A = PF6; 3c n = 3, R = H, A = BF4; 4b n = 4, R = H, A = PF6; 4c n = 4, R = H, A = BF4; 5b n = 3, R = CH3, A = PF6; 5c n = 3, R = CH3, A = BF4.
Reaction of 1a - 4a with a molecular equivalent of HPF6 or NaBF4 affords the imidazolium salts [1-alkylnitrile-3-methylimidazolium][PF6] (n = 1 - 4) 1b - 4b and [1- alkylnitrile-3-methylimidazolium][BF4] (n = 1 - 4) 1c - 4c, respectively. The imidazolium salts [1-alkylnitrile-3-methylimidazolium]PF65b and [1-alkylnitrile-3- methylimidazolium]BF45c are prepared from 5a using an analogous method. For 1b - 5b the salts are washed with water in order to remove the hydrogen chloride formed during the anion exchange reaction, whereas tetrohydrofuran and diethyl ether are used to wash 1c - 5c. The salts are then dried under vacuum for 1 - 2 days. The salts 2c, 3c, 4a, 4b and 3c are liquid at room temperature and are further purified by filtration through silica and left under vacuum at 40 - 50°C for several days. All the imidazolium salts are obtained in medium to high yield. They are stable in air and show no signs of decomposition up to 150°C. Some of the ionic liquids within the scope of this invention are listed in the examples and appendix).
The synthetic route to prepare ionic liquids with a functionalized anion involves the preparation of the anion as a potassium salt, followed by anion metathesis with various imidazolium halides. The synthesis of e.g. K[BF3CHCH3CH2CN]" is depicted in Scheme 2. The first step of the anion synthesis involves hydroboration of allyl cyanide using boron trichloride and triethylsilane, then addition of water to afford the boronic acid wich is subsequently stirred with KHF2 in ether/H2O at ambient temperature. The product, K[BF3CHCH3CH2CN]" 1, is recrystallized from acetone on addition of diethyl ether as colourless needles in 74% yield. Surprisingly alpha-alkene hydroboration affords boronic esters or acids at the alpha-position.
Commencing with 1-methylimidazole or 1-trimethylsylilimidazole a series of imidazolium halides 2-10 were prepared. Subsequent metathesis with 1 in acetone give the dual- functionalized ionic liquids 11 - 19 in yield of 80 to 90%.
Scheme 2
3
Figure imgf000008_0001
Scheme 2 Synthesis of 'dual-iunctionahsed' ionic liquids with the [BF3CHCH3CH2CN] anion
USES OF THE IONIC LIQUIDS
These ionic liquids can react with lanthanide and actinide series and transition metal chlorides and other metal salts or compounds used as catalysts to form complexes, for example, with PdCI2, PtCI2, RuCI3, RhCI3, and [Ru(arene)CI2]2- Included within the term salts are not only the chlorides, but other salts which are known and employed to those skilled in the art. Metal containing molecular compounds used as catalysts, e.g. Wilkinson's catalyst and Grubb's catalyst, or the like can also be employed in this invention.
The process of making the complex is a straightforward one of dissolving a catalytically effective amount of the desired catalyst in enough of the ionic liquid to form a solution. If the catalyst and ionic liquid solution is to be used immediately in a catalyzed reaction, the amounts of the two can be those required for the reaction, the ionic liquid serving as solvent for the reaction step immediately following. The reaction product usually is separated from the reactants by solvent extraction, but the immobilized catalyst remains in the ionic liquid solvent, so is recovered and can be used for another reaction. The catalyst can also be prepared in a concentrated form in the ionic liquid , then later diluted with an excess of the ionic liquid to the desired catalyst concentration.
Since these complexes form part of the liquid, they are highly soluble in the ionic liquid. Many will catalyze a wide range of organic transformations, like hydrogenation, hydroformylation, metathesis, C-C coupling reactions, dimerization, oligomerization and polymerization.
The main advantages of the invention are: 1. The ionic liquids act as both ligand and solvent when used as media for organic synthesis in multiphasic catalysis, therefore, no other ligands are necessary. 2. The catalysts are strongly immobilized in the ionic liquids and can be easily recycled without loss (or minimal loss) of the catalyst.
The dual-functionalized ionic liquids are particularly advantageous due to their very low viscosities, e.g. as shown in Examples 33 to 35. As noted above, the nitrile derivatized ionic liquids of this invention are useful as solvents for multiphasic catalysis, in terms of catalyst retention and product separation. Dissolution of PdCI2 in [C3CNmim][BF4] 3c affords [Pd(NCC3mim)2CI2][BF4]2 in quantitative yield. The resulting solution is used to hydrogenate 1 ,3,-cyclohexadiene under biphasic conditions, which affords cyclohexene and cyclohexane. The overall conversion is 90% and the turnover frequency 247 molmol"1h"1; cyclohexene is formed with a selectivity of 97%. This is possibly because the monoene dissociates from the catalyst and is less soluble in the ionic liquid than the diene, which is therefore hydrogenated in preference. Hydrogenation reactions have been widely studied in ionic liquids, including the substrate 1 ,3-cyclohexadiene, but this would appear to be the first time selectivity to cyclohexene has been observed. Selective hydrogenation of 1,3- cyclohexadiene using palladium and platinum complexes with chiral ferrocenylamine sulfide and selenide ligands has been reported previously. It is clearly an advantage that the palladium ionic liquids system gives such selectivity without the need for aditional co- ligands. However, the most important feature of this system is that the catalyst is part of the ionic liquid and therefore not easily lost during extraction of the product. No decrease in activity is observed after re-use of the catalyst solution. No palladium residues in the organic phase are detected using inductively coupled plasma analysis.
This invention is illustrated by the following examples.
EXAMPLES
The following examples are given to illustrate the synthesis of these ionic liquids and application in catalysis.
The 1-methylimidazole and 1 ,2-dimethylimidazole and chloronitriles are purchased from Fluka, HPF6 and NaBF are purchased from Aldrich and are used as received without further purification. The synthesis of the imidazolium salts 1a - 5a is performed under an inert atmosphere of dry nitrogen using standard Schlenk techniques in solvents dried using the appropriate reagents and distilled prior to use. All other compounds are made without precautions to exclude air or moisture. IR spectra are recorded on a Perkin-Elmer FT-IR 2000 system. NMR spectra are measured on a Bruker DMX 400, using SiMe4 for 1H, 85% H3PO4 for 31P, as external standards at 20°C. Electrospray ionization mass spectra (ESI-MS) are recorded on a ThermoFinnigan LCQ™ Deca XP Plus quadrupole ion trap instrument on sample diluted in methanol.19 Samples are infused directly into the source at 5 μL min"1 using a syringe pump and the spray voltage is set at 5 kV and the capillary temperature at 50°C. Samples 2c, 3c, 4a, 4b and 4c are purified by filtration through silica and left under vacuum (ca. 0.1 mm Hg) at 40 - 50°C in order to remove traces of salt impurities and volatile components. Differential scanning calorimetry is performed with a SETARAM DSC 131. Density is determined with a picometer at room temperature (20 ± 1 °C) on 1.0 ml of sample. The measurements are repeated three times and average values are used. Viscosities are measured with a Brookfield DV-II+ viscometer on 0.50 ml of sample. The temperature of the samples is maintained to 25 ± 1°C by means of an external temperature controller. The measurements are performed in duplicate.
EXAMPLE 1. Synthesis o/" 1-methylnitrile-3-methylimidazolium7C7 1a A mixture of 1-methylimidazole (8.21 g, 0.10 mol) and CICH2CN (9.06 g, 0.12 mol) is stirred at room temperature for 24 hours, during which time the reaction mixture turned to a solid. The solid is washed with diethyl ether (3 x 30 ml) and dried under vacuum for 24 hours, yield: 14.5 g, 92%; M.p. 170°C. Crystals suitable for X-ray diffraction are obtained by slow diffusion of ethyl ether into an acetonitrile solution of the compound at room temperature. ESI-MS (CH3OH): positive ion: 122 [CCNmim], negative ion: 35 [CI]. 1H NMR (D2O): δ= 9.06 (s, 1 H), 7.72 (s, 1 H), 7.61 (s, 1 H), 4.65 (s, 2H), 3.96 (s, 3H). 13C NMR (D2O): δ= 140.40, 127.65, 125.52, 117.02, 74.82, 39.54. IR (cm"1): 3177, 3126, 3033 (vc.H aromatic), 2979, 2909, 2838, 2771 (vc.H aliphatic), 2261 (vc≡N), 1769 (vc=N)- Anal. Calcd for C6H8CIN3 (%): C 45.73, H 5.12, N 22.66; Found: C 45.86, H 5.26, N 22.58.
EXAMPLE 2. Synthesis of '1-methylnitrile-3-methylimidazoliurn/PF6 1b To a solution of 1a (4.73 g, 0.03 mol) in water (50 ml), HPF6 (8.03 g, 60 wt%, 0.033 mol) is added at room temperature. After 10 minutes the solid that had formed is collected by filtration and washed with ice-water (3 x 15 ml) and then dried under vacuum. Yield: 5.61 g, 70%; M.p. 78°C. ESI-MS (CH3OH): positive ion: 122 [CCNmim], negative ion: 145 [PFβ]. 1H NMR (CD3CN): δ= 8.59 (s, 1 H), 7.53 (s, 1 H), 7.44 (s, 1H), 5.41 (s, 2H), 3.86 (s, 3H). 13C NMR (CD3CN): δ= 139.9, 127.6, 125.5, 120.5, 40.0, 39.3. 3 P NMR (CD3CN): - 145.25 (hept). IR (cm'1): 3180, 3133, 3027 (vc.H aromatic), 2983, 2938 (vc.H aliphatic), 2274 (vc≡N), 1602 (vc= ). Anal. Calcd for C6H8N3F6P (%): C 26.98, H 3.02, N 15.73; Found: C 27.02, H 3.09, N 15.66.
EXAMPLE 3. Synthesis of [1-methylnitrile-3-methylimidazoliunr /BF4 1c A mixture of 1a (4.73 g, 0.03 mol) and NaBF4 (3.62 g, 0.033 mol) in acetone (80 ml) is stirred at room temperature for 48 hours. After filtration and removal of the solvents the resulting pale yellow waxy solid is washed with tetrohydrofuran and diethyl ether to give the product. Yield: 5.76 g, 92%; M.p. 35°C. ESI-MS (CH3OH): positive ion: 122 [CCNmim], negative ion: 87 [BF4]. 1H NMR (CD3CN): δ= 8.67 (s, 1 H), 7.56 (s, 1H), 7.47 (s, 1 H), 5.26 (s, 2H), 3.87 (s, 3H). 13C NMR (CDCI3): δ= 140.35, 127.57, 125.46, 1 16.76, 39.79, 39.21. IR (cm'1): 3171, 3124, 3015 (vc.H aromatic), 2977, 2845 (VCH aliphatic), 2253 (vc≡N), 1588 (vc=N). Anal. Calcd for C6H8BF4N3(%): C 34.48, H 3.86, N 20.11 ; Found: C 34.52, H 3.82, N 20.26.
EXAMPLE 4. Synthesis o71-ethylnitrile-3-methylimidazoliuιτι/C/ 2a A mixture of 1-methylimidazole (8.21g, 0.10 mmol) and CI(CH2)2CN (10.74 g, 0.12 mol) is stirred in toluene (20 ml) at 70°C for 24 hours. The resulting white solid is washed with diethyl ether (5 x 30 ml). The product is then dried in vacuum for 24 hours. Yield: 15.5g, 82%; M.p. 50°C. ESI-MS (CH3OH): Positive ion: 136 [C2CNmim], negative ion: 35 [CI]. 1H NMR (D2O): δ= 8.73 (s, 1H), 7.48 (s, 1 H), 7.46 (s, 1 H), 4.64 (t, J(H, H) = 6.8 Hz, 2H), 3.94 (s, 3H), 3.03 (t, J(H, H) = 6.8 Hz, 2H); 13C NMR (D20): δ= 139.58, 138.05, 126.16, 122.53, 47.86, 42.12, 38.83. IR (cm"1): 3244 (vc.H aromatic), 2916, 2788, 2700 (vc-H aliphatic), 2250 (vc=N), 1720 (vc=N). Anal. Calcd for C7H10CIN3 (%): C 48.99, H 5.87, N 24.48; Found: C 50.02, H 5.75, N 24.71.
EXAMPLE 5. Synthesis of /"1 -ethylnitrile-3-methylimidazoliumyPF6 2b The same procedure is followed as that described above for 1b, except 2a (5.15 g, 0.03 mol) and HPF6 (8.03 g, 60wt%, 0.033 mol) are used, and the product is obtained as a white solid. Yield: 6.83g, 81%; M.p. 35°C. ESI-MS (CH3OH): Positive ion: 136 [C2CNmim], negative ion: 145 [PF6]. 1H NMR (CD3CN): δ= 8.64 (s, 1H) 7.50 (s, 1 H), 7.43 (s, 1H), 4.46 (t, J(H, H) = 6.49 Hz, 2H), 3.89 (s, 3H), 3.03 (t, J(H, H) = 6.49 Hz, 2H). 13C NMR (CD3CN): δ= 139.36, 127.13, 125.34, 120.49, 47.87, 39.01 , 21.92. 31P NMR (CD3CN): -142.90 (hept). IR (cm"1): 3168, 3126, 3101 (vc.H aromatic), 2964 (vc.H aliphatic), 2255 (vc≡N), 1704 (VC=N). Anal. Calcd for C7H10F6N3P (%): C 29.90, H 3.58, N 14.95; Found: C 29.95, H 3.62, N 14.88.
EXAMPLE 6. Synthesis of 1-ethylnitrile-3-methylimidazoliurn/SF4 2c The same procedure is followed as that described above for 1c, except 2a (5.15 g, 0.03 mol) is used instead of 1a. The product is obtained as pale yellow liquid at room temperature. Yield: 5.69 g, 85%; M.p. 20°C. ESI-MS (CH3OH): Positive ion: 136 [C2CNmim], negative ion: 87 [BF4]. H NMR (CD3CN,): δ= 8.56 (s, 1 H), 7.41 (s, 1 H), 7.37 (s, 1H), 4.48 (brs, 2H), 3.88 (s, 3H), 3.05 (brs, 2H). 13C NMR (CD3CN): δ= 138.33, 126.22, 122.56, 121.04, 47.81 , 38.54, 21.81. IR (cm"1): 3165 and 3124 (vc.H aromatic), 2955 and 2855 (vc.H aliphatic), 2251 (vc=N), 1736 (vc= ). Anal. Calcd for C7H10N3BF4 (%): C 37.70, H 4.52, N 18.84; Found: C 37.52, H 4.65, N 19.05.
EXAMPLE 7. Synthesis of/l-propylnitrile-3-methylimidazoliurn/C/ 3a A mixture of 1-methylimidazole (8.21g, 0.10 mmol) and CI(CH2)3CN (12.43g, 0.12 mol) is stirred at 80°C for 24 hours. The resulting white solid is washed with diethyl ether (3 * 30 ml). The product is dried in vacuum for 24 hours. Yield: 17.6 g, 95%; M.p. 80°C. ESI-MS (CH3OH): Positive ion: 150 [C3CNmim], negative ion: 35 [CI]. 1H NMR (CDCI3): δ= 8.73 (s, 1 H), 7.45 (s, 1 H), 7.39 (s, 1H), 4.27 (t, J(H, H) = 6.8 Hz, 2H), 3.82 (s, 3H), 2.50 (t, J(H, H) = 6.8 Hz, 2H), 2.20 (t, J(H, H) = 6.8 Hz, 2H). 13C NMR (CDCI3): δ= 134.11 , 130.49, 120.01 , 116.19, 44.01 , 30.87, 21.21 , 9.87. IR (cm"1): 3373, 3244, 3055 (vc-H aromatic), 3029, 2974, 2949, 2927 (vc-H aliphatic), 2243 (vc=N), 1692 (vc=N). Anal. Calcd for C8H12CIN3 (%): C, 51.76, H, 6.51 , N, 22.63; Found: C 51.72, H 6.55, N 22.71.
EXAMPLE 8. Synthesis of "1-propylnitrile-3-methylimidazolium;PF6 3b The same procedure is followed as that described above for 1b, except 3a (5.57 g, 0.03 mol) is used instead of 1a. The product is obtained as white solid. Yield: 6.90 g, 78%; M.p. 75°C. ESI-MS (CH3OH): Positive ion: 150 [C3CNmim], negative ion: 145 [PF6]. 1H NMR (CDCI3): δ= 8.63 (s, 1H), 7.59 (s, 1H), 7.55 (s, 1 H), 4.42 (t, J(H, H) = 7.0 Hz, 2H), 4.03 (s, 3H), 2.66 (t, J(H, H) = 7.0 Hz, 2H), 2.33 (m, 2H). 3C NMR (CDCI3): δ= 135.50, 131.80, 120.10, 116.50, 44.25, 33.30, 22.50, 9.98. 31P NMR (CDCI3): -145.90 (hept). IR (cm"1): 3171, 3158, 3128 (vc.H aromatic), 2980, 2807 (vc.H aliphatic), 2246 (vc=N), 1696 ((VC=N). Anal. Calcd for C8H12F6N3P (%): C 32.55, H 4.10, N 14.24; Found: C 32.59, H 4.1 1 , N 14.30.
EXAMPLE 9. Synthesis of [1-propylnitrile-3-methylimidazoliurn/SF4 3c The same procedure is followed as that described above for 1c, except 3a (5.57 g, 0.03 mol) is used instead of 1a. Yield: 6.4 g, 90%; M. p. -71.9°C. ESI-MS (CH3OH): Positive ion: 150 [C3CNmim], negative ion: 87 [BF4]. 1H NMR (CDCI3): δ= 9.32 (s, 1 H), 8.18 (s, 1 H), 8.14 (s, 1 H), 4.96 (brs, 2H), 4.54 (s, 3H), 3.20 (brs, 2H), 2.85 (brs, 2H). 13C NMR (CDCI3): δ= 135.03, 131.17, 120.69, 116.71 , 44.69, 33.78, 22.01 , 10.15. IR (cm"1): 3161 , 3121 (vc-H aromatic), 2971 (vc.H aliphatic), 2249 (vc≡N), 1712 (vc=N). Anal. Calcd for C8F4BH12N3 (%): C 40.54, H 5.10, N 17.73; Found: C 40.58, H 5.13, N 17.69.
EXAMPLE 10. Synthesis of /'1-butylnitrile-3-methylirnidazoliurn/C/ 4a A mixture of 1-methylimidazole (8.21g, 0.10 mmol) and CI(CH2)4CN (14.1g, 0.12 mol) is stirred at 80°C for 4 hours. The temperature is then increased to 110°C and the reaction mixture is stirred at for further 2 hours. After cooling, the reaction mixture is washed with diethyl ether (3 *15 ml) and dried under vacuum for 24 hours. The product is obtained as viscous brownish liquid. Yield: 17.9 g, 90%; M.p. 32°C. ESI-MS (CH3OH): Positive ion: 164 [C4CNmim], negative ion: 35 [CI]. 1H NMR (CD3CN): δ= 9.99 (s, 1 H), 7.75 (s, 1 H), 7.70 (s, 1H), 4.41 (t, J(H, H) = 7.2 Hz, 2H), 3.94 (s, 3H), 2.57 (t, J(H, H) = 7.0 Hz, 2H), 2.07 (m, J(H, H) = 6.8 Hz, 2H), 1.64 (m, J(H, H) = 6.8 Hz, 2H). 13C NMR (CD3CN): δ = 134.22, 129.29, 127.97, 125.81 , 123.18, 41.50, 34.43, 27.47, 21.77. IR (cm'1): 3138, 3088, 3082 (vc.H aromatic), 2948 (vc.H aliphatic), 2241 (vc=N), 1701 ((vc=N). Anal. Calcd for C9H14CIN3 (%): C 54.13, H 7.07, N, 21.04; Found: C 54.21 , H 7.09, N, 21.09.
EXAMPLE 11. Synthesis o/71-butylnitrile-3-methylimidazoliurn/PF6 4b The same procedure is followed as that described above for 1b, except 4a (5.99 g, 0.03 mol) is used instead of 1a. The product is obtained as brown liquid at room temperature. Yield: 7.6 g, 82%; M.p. -60.3°C. ESI-MS (CH3OH): positive ion: 164 [C3CNmim], negative ion: 145 [PF6]. H NMR (CD3CN): δ= 8.45 (s, 1 H), 7.38 (s, 1H), 7.35 (s, 1 H), 4.15 (t, J(H, H) = 7.17 Hz, 2H), 3.83 (s, 3H), 2.44 (t, J(H, H) = 7.17 Hz, 2H), 1.93 (m, J(H, H) = 7.17, 2H), 1.64 (m, J{H, H) = 7.17, 2H). 13C NMR (CD3CN): δ= 138.95, 126.72, 125.16, 122.85, 120.80, 38.78, 31.61 , 24.74, 18.93. 31P NMR (CDCI3): -140.80 (hept). IR (cm"1): 3168, 3123 (vc.H aromatic), 2972, 2901 (vC-H aliphatic), 2250 (vc=N), 1577 ((vc.N). Anal. Calcd for C9F6H14N3P (%): C 34.96, H 4.56, N 13.59; Found: C 35.05, H 4.41 , N 13.64.
EXAMPLE 12. Synthesis of /'1-butylnitrile-3-methylimidazolium./SF44c The same procedure is followed as that described above for 1c, except 4a (5.99 g, 0.03 mol) is used instead of 1a. The product is obtained as brown liquid at room temperature. Yield: 6.4 g, 85%; M.p. -71.9°C. ESI-MS (CH3OH): Positive ion: 164 [C3CNmim], negative ion: 87 [BF4]. 1H NMR (CD3CN): δ= 8.54 (s, 1H), 7.43 (s, 1H), 7.39 (s, 1H), 4.17 (brs, 2H), 3.83 (s, 3H), 2.44 (brs, 2H), 1.92 (brs, 2H), 1.60 (brs, 2H). 3C NMR (CD3CN): δ= 139.24, 131.19, 128.02, 126.68, 123.72, 38.69, 31.64, 24.70, 18.64. IR (cm"1): 3161, 3120 (vc.H aromatic), 2955, 2876 (vc.H aliphatic), 2247 (vc=N), 1575 (vc=N). Anal. Calcd for C9H14N3BF4 (%): C 43.06, H 5.62, N 16.74; Found: C 43.12, H 5.53, N 16.70.
EXAMPLE 13. Synthesis of /'1-methylnitrile-2,3-dimethylimidazolium7C/ 5a A mixture of 1 ,2-dimethylimidazole (9.61 g, 0.10 mol) and CI(CH2)3CN (12.43 g, 0.12 mol) is stirred at 100°C for 24 hours. Two phases are formed at the end of the reaction. The upper phase is decanted and the lower phase is washed with diethyl ether (3 * 30 ml). A pale yellow solid is formed during the washing and the product is dried in vacuum for 24 hours at room temperature. Yield: 18.6 g, 93%; M.p. 105°C. x (CH3OH): Positive ion: 164 [C3CNdimim], negative ion: 35 [CI]. 1H NMR (CD3CN): δ= 7.50 (s, 1H), 7.31 (s, 1H), 4.14 (t, J(H, H) = 7.17 Hz, 2H), 3.71 (s, 3H), 2.53 (s, 3H), 2.46 (t, J(H, H) = 7.17 Hz, 2H), 2.11 (m, J(H, H) = 7.17 Hz, 2H). 13C NMR (CD3CN): δ= 125.52, 123.70, 122.32, 120.73, 49.47, 37.66, 28.12, 16.50, 11.92. IR (cm"1): 3182, 3098, 3046 (vc.H aromatic), 2989, 2898, 2834 (vc.H aliphatic), 2240 (vCεN), 1631 (vc=N). Anal. Calcd for C9H14CIN3 (%): C 54.13, H 7.07, N 21.04; Found: C 54.18, H 7.17, N 20.92.
EXAMPLE 14. Synthesis of 1-methylnitrile-2,3-dimethylimidazolium;PF6 5b The same procedure is followed as that described above for 1b, except 5a (5.99 g, 0.03 mol) is used instead of 1a. The product is obtained as white solid at room temperature. Yield: 7.33 g, 79%; M.p. 85°C. ESI-MS (CH3OH): Positive ion: 164 [C3CNdimim], negative ion: 145 [PF6]. 1H NMR (CD3CN): δ= 7.34 (s, 1 H), 7.32 (s, 1 H), 4.18 (t, J(H, H) = 7.17 Hz, 2H), 3.75 (s, 3H), 2.55 (s, 3H), 2.51 (t, J(H, H) = 7.17 Hz, 2H), 2.14 (m, J(H, H) = 7.17, 2H). 13C NMR (CD3CN): δ= 144.91 , 122.87, 120.99, 120.59, 46.85, 35.08, 25.02, 14.09, 9.37. 31P NMR (CD3CN): -140.80 (hept). IR (cm'1): 3150 (vc-H aromatic), 2966 ( OH aliphatic), 2249 (vc≡N), 1628 (vc=N). Anal. Calcd for C9F6H14N3P (%): C 34.96, H 4.56, N 13.59; Found: C 35.02, H 4.52, N 13.61.
EXAMPLE 15. Synthesis of /1-methylnitrile-2,3-dimethylimidazolium;BF45c The same procedure is followed as that described above for 1c, except 5a (5.99 g, 0.03 mol) is used instead of 1a. The product is obtained as white waxy solid at room temperature. Yield: 6.77 g, 90%; M.p. 40°C. ESI-MS (CH3OH): Positive ion: 164 [C3CNdimim], negative ion: 87 [BF4]. 1H NMR (CD3CN): δ= 7.31 (s, 1 H), 7.30 (s, 1 H), 4.15 (t, J(H, H) = 6.84 Hz, 2H), 3.72 (s, 3H), 2.59 (s, 3H), 2.47 (t, J(H, H) = 6.84, 2H), 2.13 (m, J(H, H) = 6.84, 2H). 13C NMR (CD3CN): δ= 125.54, 123.70, 122.08, 120.52, 49.51 , 37.71 , 28.04, 16.59, 11.98. IR (cm'1) 3185, 3145 (vc-H aromatic), 2966 (vc.H aliphatic), 2244 (vc≡N), 1701 ((vc=N). Anal. Calcd for C9H14BF4N3 (%): C 43.06, H 5.62, N 16.74; Found: C 42.85, H 5.75, N 16.68.
EXAMPLE 16. Synthesis of /■Po, 1-methylnitrile-2,3-dimethylimidazoliumJ2C/27/'βF 2 A mixture of 5c (153 mg, 0.61 mmol) and palladium chloride (54 mg, 0.305 mmol) in 5.0 ml dichloromethane is stirred at room temperature for 3 days. The resulting yellow solid is extracted by filtration, washed with diethyl ether (2 x 5.0 ml) and dried in vacuum. Yield: 195 mg, 94%; M.p.: 130°C; 1H NMR (DMSO): δ= 7.62 (s, 1 H), 7.61 (s, 1H), 4.16 (t, J(H, H) = 7.17 Hz, 2H), 3.72 (s, 3H), 2.57 (s, 3H), 2.56 (brs, 3H), 2.06 (m, J{r , H) = 7.17 Hz,2H); 13C NMR (DMSO): δ= 148.10, 125.91 , 124.20, 123.16, 49.61 , 38.09, 28.39, 16.81 and 12.60; Anal. Calcd for C18H28B2CI2F8N6Pd (%): C 31.82, H 4.15, N 12.37; Found: C 31.75, H 4.10, N 12.34; IR (cm'1): 3152 and 3120 (vc-H aromatic), 2988, 2973 and 2901 (vc.H aliphatic), 2325 (vc=N), 1692 ((vc=N).
EXAMPLE 17. Synthesis of[1-cyanopropyl-3-methylimidazolum]2[PdCI4] A reaction mixture of PdCI2 (177 mg, 1.0 mmol) and 3a (377 mg, 2.00 mmol) in dichloromethane (2 ml) is stirred at r.t. for 4 days. The resulting orange solid is collected by centrifugation and washed with dichloromethane (20 ml). Drying in vacuum gave the product in pure form. Yield: 548 mg, 100%. Mp: 178°C. 1H NMR (DMSO-d6): 2.18 (t, 2H), 2.64 (t, 2H), 3.89 (s, 3H), 4.32 (t, 2H), 7.79 (s, 1H), 7.87 (s, 1H), 9.37 (s, 1H). 13C NMR (DMSO-d6): 135.28, 131.36, 120.13, 116.18, 44.02, 31.22, 21.77, 9.99. Microanalysis: Found (Calc): C 35.03 (35.07), H 4.41 (4.44), N 15.32 (15.29)%. IR (cm"1): uCN, 2241 (s). The compound could be dissolved in ionic liquids and used as a catalyst, the results in the hydrogenation of 1 ,3-cyclohexadiene are similar to those obtained in EXAMPLE 19.
EXAMPLE 18. Synthesis of[(1-cyanopropyl-3-methylimidazolum)2PdCl2][BF4]2 A reaction mixture of PdCI2 (177 mg, 1.0 mmol) and (474 mg, 2.00 mmol) [C3CNmim][BF4] 3c in dichloromethane (2 ml) is stirred at room temperature for 4 days. The resulting pale yellow solid is collected by centrifugation and washed with dichloromethane (20 ml). Drying in vacuum gave the product in pure form. Yield: 99%. M.p.: 80°C. 1H NMR (DMSO-d6): 2.18 (m, 2H), 2.58 (t, 2H), 3.86 (s, 3H), 4.25 (t, 2H), 7.71 (s, 1H), 7.77 (s, 1H), 9.09 (s, 1 H). 13C NMR (DMSO-d6): 132.12, 120.15, 118.69, 116.09, 44.08, 33.35, 27.87, 9.84. Microanalysis: Found (Calc): C 29.51 (29.50), H 3.74 (3.71 ), N 12.88 (12.90)%. IR (cm"1): 3159, 3112 (vc.H aromatic), 2933 (vc.H aliphatic), 2324 (VC=N), 1721 (VC=N); this compound can be dissolved in ionic liquids and used as a catalyst, the results in the hydrogenation of 1 ,3-cyclohexadiene are similar to those obtained in EXAMPLE 19.
EXAMPLE 19. Hydrogenation of 1 ,3-cyclohexadiene by PdCI2 in 3c PdCI2 (~5 mg) is dissolved in ionic liquid 3c (1 ml), and 1 ,3-cyclohexadiene (1 ml) is added. The reaction is pressurized with H2 to 45 atm, sealed and heated to 100°C for 4 h which gave cyclohexene in 90% yield. The product is simply removed by decantation and no palladium is detected (based on ICP analysis).
EXAMPLE 20 Comparison of Suzuki reactions carried out in [C4mim][BF4] and [C3CNmim][BF4] (depicted in Scheme 3)
Scheme 3
Figure imgf000018_0001
R = H 3a, R = CH3 5a R = H 6a, R - CH3 7a
R = H, X = PF6 3b, R = CH3, X - PF6 5b R - H, X = BF4 3c, R = CH3, X = BF45c
Figure imgf000018_0002
CH2C12
R = H, X - PF6 6b, R - CH3, X - PF6 7) R = H, X - BF4 6c, R - CH3, X = BF4 7
Figure imgf000018_0003
Complexes 7a, 7b, 7c are used for Suzuki coupling reaction of iodobenzene and benzeneboronic acid, as shown in scheme 2, above, lodobenzene (2.5 mmol, 1 equiv.), benzenboronic acid (2.75 mmol, 1.1 equiv.), Na2CO3 (560 mg, 5.28 mmol, 2.1 equiv.), palladium complex (0.03 mmol) and water (2.5 ml) are mixed with [C4mim][BF4] (5 ml). The mixture is heated to 110°C with vigorous stirring for 12 hours, then cooled and extracted with diethyl ether (3 * 15 ml). The combined organic phase is dried over MgSO4 and filtered. The product, biphenyl, is obtained in 100% yield. If a nitrile ionic liquid, [C3CNmim][BF4], is used in place of the [C mim][BF4], a similar yield is obtained. Significantly, using [C3CNmim][BF4] the yields can be maintained at above 90% even after six runs of catalysis, while yields decrease rapidly for [C4mim][BF4]. Dissolving PdCI2 in the [C3CNmim][BF4] gives the same result as using complexes 6 and 7. Examples 21 to 32 describe the dual-functionalized ionic liquids with the [BF3CHCH3CH2CN]' anion.
Example 21 Synthesis of 3 (R = CH2CH=CH2, X = Br)
A mixture of 1-methylimidazole (8.21 g, 0.10 mol) and propenyl bromide (12.1 g, 0.10 mol) in methanol (50 ml) is stirred at room temperature for 5 days. The solvent is removed under reduced pressure. The resulting pale yellow viscous liquid is washed with diethyl ether (3 x 100 ml) and then dried in vacuum. Yield: 18.67g, 92%; m.p.: - 52.5°C; ESI-MS (H2O, m/z): positive ion, 123, [CH2CH=CH2mim]+; negative ion, 80, [Br]"; 1H NMR (D2O): <5 8.79 (s, 1H), 7.62 (s, 1 H), 7.60 (s, 1H), 6.15 (m, 1 H), 5.50 (m, 1H), 4.96 (m, 2H), 4.05 (s, 3H); 13C NMR (D2O): 136.1 , 130.7, 124.5, 122.8, 121.5, 51.8, 36.3; Anal. Calcd. for C7HnN2Br (%): C 41.40, H 5.46, N, 13.79; Found: C 40.41 , H 5.41 , N 13.27.
Example 22 Synthesis of 7 (R = CH2CH=CH2, X = Br)
A mixture of 1-allylimidazole (10.8 g, 0.10 mmol) and propenyl bromide (12.1 g, 0.10 mol) in methanol (50 ml) is stirred at room temperature for 5 days. The solvent is removed under reduced pressure. The resulting pale yellow viscous liquid is washed with diethyl ether (3 x 30 mL). The product is dried in vacuum for 24 h. Yield: 19.3 g, 95%; m.p.: - 26.5DC. ESI-MS (H2O, m/z): positive ion, 149 [DiCH2CH=CH2im]+; negative ion, 80 [Br]'; 1H NMR (D2O): δ 9.20 (s, 1H). 7.85 (s, 2H), 6.20 (m, 2H), 5.55 (m, 4H), 5.10 (m, 4H); 13C NMR (D2O): 135.5, 130.5, 123.1 , 122.0, 51.9; Anal. Calcd. for C7HnN2Br (%): C 41.40, H 5.46, N, 13.79. Found: C 40.41 , H 5.41 , N 13.27.
Example 23 Synthesis of 10 (R = CH2CH2CH2C≡N, X = CI)
A mixture of trimethysilyimidazole (14.03 g, 0.10 mol) and CI(CH2)3CN (24.86 g, 0.24 mol) wis stirred at 80°C for 24 h. The resulting white solid is washed with diethyl ether (3 x 30 mL). The product is dried in vacuum for 24 h. Yield: 22.4 g, 94%; m.p.: 100DC. ESI- MS (H2O, m/z): positive ion, 203 [Di(CH2)3C≡Nim]+; negative ion, 35, 37 [CI]"; 1H NMR (D2O): δ 8.56 (s, 1 H), 7.52 (s, 2H), 4.48 (t, 4H, 3 (H, H) = 7.15 Hz), 2.66 (m, 4H), 2.35 (t, 4H, 3J(H, H) = 7.15 Hz); 3C NMR (D20): 137.10, 123.4, 119.2, 48.3, 29.3, 25.1 ; IR (cm" 1): 3166, 3075, 2939, 2895, 2839, 2241 , 1781 , 1669, 1570, 1559; Anal. Calcd for CnH15CIN4 (%): C 55.35, H 6.33, N 23.47. Found: C 54.98, H 6.08, N 23.55. Example 24 Synthesis of 11 (R, = CH2CH2CH2CH3, R2 = CH3)
A mixture of 1 (1.0 g, 5.71 mmol) and 2 (1.0 g, 5.71 mmol) is stirred in acetone at room temperature for 24 h. The resulting suspension is filtered and the filtrate dried in vacuum. The resulting ionic liquid is purified by washing with diethyl ether, and the solvents removed in vacuo. Yield: 1.32 g, 84%. Pale yellow liquid, m.p.: - 84.5°C; ESI-MS (H20, m/z) positive ion, 139, [C4mim]+; negative ion, 136, [CH3(BF3)CHCH2CN]"; 1H NMR (d6- acetone): δ 8.28 (s, 1 H), 7.16 (s, 1H), 7.11 (s, 1H), 4.45 (t, 3J(H, H) = 7.15 Hz, 2H), 3.85 (s, 3H), 2.35-1.94 (m, 4H), 1.92-1.85 (m, 2H), 1.32 (t, 3H, 3J(H, H) = 6.98 Hz), 1.20 (m, 2H), 0.89 (d, 3H, 3J(H, H) = 7.3 Hz), 0.56 (m, 1 H); 13C NMR (d6-acetone): δ 136.8, 126.3, 124.5, 121.7, 49.0, 35.7, 31.9, 29.2, 20.6, 19.6, 15.5, 13.0; 9F NMR (d6-acetone): -149.8 (m); IR (cm"1): 3154, 3117, 2962, 2872, 2239, 1574; Anal. Calcd. for C12H2ιBF3N3 (%): C 52.39, H 7.69, N, 15.27. Found: C 52.38, H 7.41 , N 15.51.
Example 25 Synthesis of 12 (R, = CH2CH=CH2, R2 = CH3)
The same method is used as in the synthesis of 11 except 3 (1.16 g, 5.71 mmol) is used in place of 2. Yield: 1.30 g, 88%. Pale yellow liquid, m. p.: -89.2°C; ESI-MS (H2O, m/z): positive ion, 123, [CH2CH=CH2mim]+; negative ion, 136, [CH3(BF3)CHCH2CN]"; 1H NMR (d6-acetone): δ 8.89 (s, 1 H), 7.67 (s, 1 H), 7.66 (s, 1 H), 6.07 (m, 1 H), 5.58 (m, 1H), 4.92 (m, 1 H), 4.61 (s, 3H), 3.95 (s, 2H), 2.34 (dd, 1H, 2J(H, H) = -17.1 Hz, 3J(H, H) = 4.3 Hz), 1.96 (dd, 1 H, 2J(H, H) = -17.1 , 3J(H, H) = 10.7 Hz), 0.87 (d, 3H, 3 (H, H) = 7.3 Hz), 0.54 (m, 1 H); 13C NMR (d6-acetone): 139.01 , 136.7, 124.89, 122.7, 121.5, 121.7, 51.3, 35.9, 28.5, 20.2, 14.8; 19F NMR (d6-acetone): -147.4 (m); IR (cm'1): 3151 , 3114, 1647, 2943, 2865, 2238, 1708, 1647, 1574; Anal. Calcd. for CnH17BF3N3 (%): C 51.00, H 6.61 , N, 16.22; Found: C 51.21 , H 6.45, N 16.17.
Example 26 Synthesis of 13 (Rn = CH2C≡CH, R2 = CH3)
The same method is used as in the synthesis of 11 except 4 (1.15 g, 5.71 mmol) is used in place of 2. Yield: 1.20 g, 82%. Pale yellow liquid, m.p.: -80.4°C; ESI-MS (H20, m/z): positive ion, 121 , [CH2C≡CHmim]+; negative ion, 136, [CH3(BF3)CHCH2CN]'; 1H NMR (d6-acetone): δ 9.49 (s, 1 H). 7.87 (s, 1 H), 7.58 (s, 1 H), 5.40 (d, 2H, 4J(H, H) = 2.80 Hz), 4.37 (s, 3H), 3.21 (d, 4H, 4J(H, H) = 2.80 Hz); 2.36 (dd, 1H, 2 (H, H) = -17.1 Hz, 3J(H, H) = 4.3 Hz), 1.91 (dd, 1H, 2J(H, H) = -17.1 , 3J(H, H) = 10.7 Hz), 0.89 (d, 3H, 3J(H, H) = 7.3 Hz), 0.54 (m, 1H); 13C NMR (acetone): δ 137.2, 124.2, 122.2, 121.2, 78.2, 75.2, 35.9, 29.3, 28.7, 20.5, 15.1 ; 19F NMR (d6-acetone): -148.8 (m); IR (cm'1): 3252, 3156, 3116, 2960, 2867, 2238, 2131 , 1697, 1625, 1576, 1459, 1425; Anal. Calcd. for CnH^BFsNa (%): C 51.40, H 5.88, N, 16.35. Found: C 51.21 , H 5.75, N 16.32.
Example 27 Synthesis of 14 (R^ = CH2CH2CH2COOH, R2 = CH3)
The same method is used as synthesis of 11 except 5 (1.17 g, 5.71 mmol) is used in place of 2. Yield: 1.53 g, 88%. Colourless liquid, m.p.: -58.6°C; ESI-MS (H2O, m/z): positive ion, 169, [CH2CH2CH2COOHmim]+; negative ion, 136, [CH3(BF3)CHCH2CN]"; 1H NMR (d6-acetone): δ 10.33 (br, 1H), 9.01 (s, 1H), 7.75 (s, 1H), 7.72 (s, 1 H), 4.35 (t, 2H, 3J(H, H) = 7.05 Hz), 4.00 (s, 3H), 2.17 (t, 2H, 3J(H,H) = 7.05), 2.39-1.96 (m, 2H), 0.89 (d, 3H, 3 (H, H) = 7.3 Hz), 0.55 (m, 1 H); 13C NMR (d6-acetone): δ = 173.7, 136.0, 124.6, 121.1 , 48.46, 35.1 , 30.9, 28.9, 20.5, 15.1 ; 19F NMR (d6-acetone): -148.8 (m); IR (cm"1): 3155, 3117, 2943, 2867, 2238, 1728, 1566, 1460; Anal. Calcd. for C12H19BF3N3θ2 (%): C 47.24, H 6.28, N, 13.77; Found: C 471.21 , H 6.75, N 13.32.
Example 28 Synthesis of 15 (RT = CH2CH2CH2C=N, R2 = CH3)
The same method is used as in the synthesis of 11 except 6 (1.06 g, 5.71 mmol) is used in place of 2. Yield: 1.39 g, 85%. Pale yellow liquid, m.p.: -76.6°C; ESI-MS (H20, m/z): positive ion, 150 [CH2CH2CH2CNmim]+; negative ion, 136, [CH3(BF3)CHCH2CN]'; 1H NMR (d6-acetone): δ = 8.75 (s, 1H), 7.44 (s, 1H), 7.39 (s, 1 H), 4.45 (t, 2H, 3J(H, H) = 7.15 Hz), 4.00 (s, 3H), 2.64 (t, 2H, 3J(H, H) = 7.15 Hz), 2.31 (t, 2H, 1 (H, H) = 7.14 Hz), 2.30 (m, 1H), 1.98 (dd, 1 H, 2J(H, H) = -17.1 , 3J(H, H) = 10.7 Hz), 0.87 (d, 3H, 3J(H, H) = 7.3 Hz), 0.55 (m, 1 H); 13C NMR (d6-acetone): 5 134.11 , 130.49, 120.0, 121.5, 116.1 , 48.0, 30.8, 28.9, 25.9, 20.5, 13.6, 9.8; 19F NMR (d6-acetone): -148.8 (m); IR (cm'1): 3156, 3116, 2960, 2866, 2239, 1631 , 1575, 1566, 1459, 1425; Anal. Calcd. for C12H18BF3N4 (%): C 50.38, H 6.34, N, 19.58; Found: C 50.21 , H 6.45, N 19.32.
Example 29 Synthesis of 16 (R, = R2 = CH2CH=CH2)
The same method is used as in the synthesis of 11 except 7 (1.31 g, 5.71 mmol) is used in place of 2. Yield: 1.43 g, 88%. Pale yellow liquid, m.p.: -87.3°C; ESI-MS (H20, m/z): positive ion, 149 [DiCH2CH=CH2im]+; negative ion, 136, [CH3(BF3)CHCH2CN]'; 1H NMR (dδ-acetone): δ 9.25 (s, 1 H). 7.86 (s, 2H), 6.11 (m, 2H), 5.45-5.35 (m, 4H), 4.99 (m, 4H), 2.31 (dd, 1 H, 2J(H, H) = -17.1 Hz, 3J(H, H) = 4.3 Hz), 1.95 (dd, 1H, 2J(H, H) = -17.1 , 3J( , H) = 10.7 Hz), 1.20 (m, 2H), 0.88 (d, 3H, 3J(H, H) = 7.3 Hz), 0.56 (m, 1H); 13C NMR (d6- acetone): δ 136.0, 131.7, 122.07, 121.7, 120.8, 51.4, 29.4, 20.6, 15.3; 19F NMR (d6- acetone): -149.8 (m); R (cm"1): 3143, 3087, 2943, 2866, 2238, 1646, 1562, 1451 , 1424; Anal. Calcd. for C13H19BF3N3(%): C 54.76, H 6.72, N, 14.74. Found: C 54.21 , H 6.85, N 14.41.
Example 30 Synthesis of 17 (R, = R2 = CH2C≡CH)
The same method is used as in the synthesis of 11 except 8 (1.03 g, 5.71 mmol) is used in place of 2. Yield: 1.38 g, 86%. Pale yellow liquid, m.p.: -55.1 °C; ESI-MS (H2O, m/z): positive ion, 145 [DiCH2C≡CHim]+; negative ion, 136, [CH3(BF3)CHCH2CN]"; 1H NMR (D2O): δ = 9.36 (s, 1H), 7.90 (s, 2H), 5.97 (d, 4H, 4J(H, H) = 4.0 Hz), 3.36 (t, 2H, 4J(H, H) = 4.0Hz), 2.35 (dd, 1 H, 2J(H, H) = -17.1 Hz, 3J(H, H) = 4.3 Hz), 1.94 (dd, 1 H, 2J(H, H) = - 17.1 , 3 (H, H) = 10.7 Hz), 0.89 (d, 3H, 3J{H, H) = 7.3 Hz), 0.56 (m, 1 H); 13C NMR (D2O): δ 138.9, 125.7, 121.7, 81.1 , 74.8, 42.5, 29.2, 20.5, 15.4; 19F NMR (d6-acetone): -149.8 (m); IR (cm'1): 3255, 3145, 2944, 2867, 2239, 2131 , 1559, 1445; Anal. Calcd. for C13H15BF3N3(%): C 55.55, H 5.38, N, 14.95; Found: C 55.21 , H 5.45, N 14.69.
Example 31 Synthesis of 18 (R, = R2 = CH2CH2CH2COOH)
The same method is used as in the synthesis of 11 except 9 (1.58 g, 5.71 mmol) is used in place of 2 as waxy solid. Yield: 1.83 g, 85%. ESI-MS (H2O, m/z): positive ion, 241 , [DiCH2CH2CH2COOHim]+; negative ion, 136, [CH3(BF3)CHCH2CN]"; 1H NMR (d6- acetone): δ 8.76 (s, 1 H), 7.44 (s, 2H), 4.08 (t, 4H, 3J(H, H) = 7.05 Hz), 2.38-2.30 (m, 1H) 2.37 (t, 4H, 3J(H, H) = 7.05 Hz), 2.08 (m, 4H), 1.97 (dd, 1 H, 2J(H, H) = -17.1 , 3J(H, H) = 10.7 Hz), 1.21 (m, 2H), 0.90 (d, 3H, 3J(H, H) = 7.3 Hz), 0.59 (m, 1 H); 13C NMR (d6- acetone): δ 179.7, 138.5, 125.5, 121.8, 51.6, 33.1 , 28.4, 27.5, 20.3, 14.9; 19F NMR (d6- acetone): -149.8 (m); IR (cm"1): 3607, 3454, 3151 , 2946, 2873, 2246, 1727, 1651 , 1565, 1460, 1421 , 1308; Anal. Calcd. for C15H23BF3N3O4(%): C 47.77, H 6.15, N, 11.14. Found: C 47.35, H 6.25, N 11.38. Example 32 Synthesis of 19 (R, = R2 = CH2CH2CH2C≡N)
The same method is used as in the synthesis of 11 except 10 (1.39 g, 5.71 mmol) is used in place of 2. Yield: 1.68 g, 87%. Colourless liquid, m.p.: - 69.8°C; ESI-MS (H2O, m/z): positive ion, 203 [Di(CH2)3C≡Nim]+; negative ion, 136, [CH3(BF3)CHCH2CN]"; 1H NMR (d6-acetone): δ 9.30 (s, 1 H), 7.83 (s, 2H), 4.46 (t, 4H, 3 (H, H) = 7.10 Hz), 2.66 (m, 4H), 2.32 (t, 4H, 3J(H, H) = 7.00 Hz), 2.34 (dd, 1 H, J{ , H) = -17.1 Hz, 3J(H, H) = 4.3 Hz), 1.99 (dd, 1H, 2J(H, H) = -17.1 Hz, 3J(H, H) = 10.7 Hz), 0.91 (d, 3H, 3J(H, H) = 7.3 Hz), 0.58 (m, 1 H); 13C NMR (d6-acetone): 137.0, 123.4, 121.9, 119.2, 48.3, 29.3, 29.1 , 25.1 , 20.6, 13.6; 19F NMR (d6-acetone): -148.8 (m); IR (cm'1): 3148, 3117, 2967, 2247, 1567, 1461, 1425; Anal. Calcd. for C15H2ιBF3N5(%): C 53.12, H 6.24, N, 20.65. Found: C 52.97, H 6.25, N 20.34.
The stability of the nitrile-functionalised anion towards catalytic hydrogenation is tested by pressurising a solution of K[CH3CH(BF3)CH2CN] (8 mg) and RuCI2(PMe3)4 (1 mg) in acetone (0.4 ml) with H2 (40 bar) at 35 °C. No reduction was observed even after 48 hours.
Example 33
Melting point data
Entry Cation Anion Melting Point (°C)
1a [CCNmim] CI 170
1b [CCNmim] PF6 78
1c [CCNmim] BF4 35
2a [C2CNmim] CI 50
2b [C2CNmim] PF6 35
2c [C2CNmim] BF4 20
3a [C3CNmim] CI 80
3b [C3CNmim] PF6 75
3c [C3CNmim] BF4 -71.9
4a [C4CNmim] CI 32
4b [C4CNmim] PF6 -60.3
4c [C4CNmim] BF4 -74.5
5a [C CNdimim] CI 105
5b [C CNdimim] PF6 85
5c [C4CNdimim] BF4 40
Example 34
Density, viscosity and solubility in common solvents
Entry Ionic liquids Density Viscosity Solubility in common solvents (g ml 1) (mpa s) H,0 Et,0 EtOH Acetone Hexane
1 [C2CNmιm][CI] 2 67 2856 miscible immiscible miscible immiscible immiscible
2 [C2CNmιm][BF4] 2 15 65 5 miscible immiscible miscible miscible immiscible
3 [C3CNmιm][BF4] 1 87 230 miscible immiscible immiscible miscible immiscible
4 [C4CNmιm][CI] 1 61 5222 miscible immiscible miscible immiscible immiscible
5 [C4CNmιm][PF6] 1 99 2181 partly immiscible immiscible miscible immiscible miscible
6 [C4CNmιm][BF4] 1 71 552 9 miscible immiscible immiscible miscible immiscible
7 [C4mιm][PF6] 1 37 320 3 partly immiscible partly miscible immiscible miscible miscible [C4mιm][BF4] 1 14 115 2 miscible immiscible immiscible miscible immiscible
Example 35
Comparison of the melting point and viscosity data of the DF-ILs with tetrafluoroborate counterparts.
Ionic liquids3 Melting Viscosity Point (°C) (cp, 20°C) 11 -84.5 101.4 [C4mim][BF4] 2 -81.0 115.2 12 -89.2 25.8 [CC=Cmim][BF4] 5b -81.1 6110 13 -80.4 175.1 14 -58.6 3047 [C3COOHmim][BF4] -58.0 4415 15 -76.6 107.5 [C3CNmim][BF4] 4 -71.9 230.0 16 -87.3 56.8 17 -55.1 1797 [DiCC=Cmim][BF4] 3 67.0 - 18 38.0 - 19 -69.8 402.4 a[C4mim][BF4]: 1-methyl-3-butylimidazolium tetrafluoroborate; [CC=Cmim][BF ]: 1-methyl-3-allylimidazolium tetrafluoroborate; [DiCC≡Cmim][BF4]: 1 ,3-di-akylimidazolium tetrafluoroborate; [C3COOHmim][BF4]: 1-methyl-3-proylcarboxylimidazolium tetrafluoroborate.

Claims

What is claimed is:
1. Chemical compounds of the general formula,
K+A',
in which K+ is a 5- or 6- membered heterocyclic ring having 1-3 hetero atoms, which can be independently N, S, or O; with the proviso that at least one of the hetero atoms must be a quatemized nitrogen atom having a -R'CN substituent, wherein R' is alkyl (Ci to Cι2); the heterocyclic ring having up to 4 or 5 substituents independently chosen from the moieties: (i) H; (ii) halogen or (iii) alkyl (CT to Ci2), which is unsubstituted or partially or fully substituted by further groups, preferably F, CI, N(CπF(2n+1.x)Hx)2, O(CnF(2n+1.x)Hx), SO2(CnF(2π+1.χ)Hχ)2 or CnF(2n+1-x)Hx where 1<n<6 and 0<x<13; and (iv) a phenyl ring which is unsubstituted or partially or fully substituted by further groups, preferably F, CI, N(CnF(2n+1.x)Hx)2, 0(CnF(2n+1.x)Hx), SO2(CnF{2n+ι.χ)Hx)2 or CnF(2n+ι-X)Hx where 1 <n<6 and 0<x<13; and A" is halide, such as chloride, bromide, fluoride and the like; BF ", PF6 ", NO3 ", CH3CO2 ' , CF3SO3 ', (CF3SO2)2N', (CF3S02)3C, CF3CO2 " or N(CN)2 ".
2. The compound of Claim 1 in which the heterocyclic ring is the pyrrolium, pyrazolium, pyridinium, pyrazinium, pyrimidinium, pyrazinium, imidazolium, thiazolium, oxazolium, or triazolium.
3. The compound of Claim 2 in which the heterocyclic ring is the pyridinium or imidazolium.
4. The compound of any one of claims 1 to 3 in which the anion is chloride.
5. The compound of any one of claims 1 to 3 in which the anion is BF4 or PF6.
6. The compound of any one of claims 1 to 3 in which the anion is BF4.
7. The chemical compounds of the general formula,
K+A',
in which K+ is a 5- or 6- membered heterocyclic ring having 1-3 hetero atoms, which can be independently N, S, or O; with the proviso that at least one of the hetero atoms must be a quatemized nitrogen atom having a -R'CN substituent, wherein R' is alkyl (Ci to Cι2); the heterocyclic ring having up to 4 or 5 substituents independently chosen from the moieties: (i) H; (ii) halogen or (iii) alkyl (d to C12), which is unsubstituted or partially or fully substituted by further groups, preferably F, CI, N(CnF(2n+ι-x)Hx)2, O(CnF(2π+ι-X)Hχ), SO2(CnF(2n .ι.χ)Hx)2 or CnF(2n+1-X)Hx where 1<n<6 and 0<x<13; and (iv) a phenyl ring which is unsubstituted or partially or fully substituted by further groups, preferably F, CI, N(CnF(2n+ι.χ)Hx)2, O(CnF(2n+ι-x)Hx), SO2(CnF(2n+ι-χ)Hx)2 or CnF(2n+ι.χ)Hχ where 1 <n<6 and 0<x<13; and A" is [BF3RCN]' wherein R' is alkyl (C, to C12).
8. The chemical compounds according to claim 7 wherein A' is [BF3CHCH3CH2CN]".
9. The use of the compounds of any one of claims 1 to 8 in the immobilization of metal catalysts, by mixing the compounds of Claim 1 with the desired amounts of lanthanide and actinide series and transition metal catalyst compounds, such as palladium and platinum chlorides PdCI2, PtCI2, RuCI3> RhCI3, or [Ru(arene)CI2]2.
10. The compound of any one of claims 1 to 8 complexed with PdCI2, PtCI2, RuCI3, RhCI3, or [Ru(arene)CI2]2.
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US7999355B2 (en) * 2008-07-11 2011-08-16 Air Products And Chemicals, Inc. Aminosilanes for shallow trench isolation films
EP2995630A1 (en) 2014-09-09 2016-03-16 Dublin Institute of Technology Hybrid compounds formed from ionic liquids and uses thereof in ion selective electrodes
CN106632056A (en) * 2016-12-27 2017-05-10 济南大学 Preparation method of single crystal of alkynyl substituted imidazole ionic liquid
EP4055025A1 (en) * 2019-11-07 2022-09-14 DSM IP Assets B.V. New transition metal catalyst
EP4651762A1 (en) 2023-01-19 2025-11-26 SharkNinja Operating LLC Hair care appliance with powered attachment
US20240245190A1 (en) 2023-01-19 2024-07-25 Sharkninja Operating Llc Identification of hair care appliance attachments
CN117327301B (en) * 2023-11-27 2024-02-13 江苏新视界先进功能纤维创新中心有限公司 An ionic liquid and its preparation method and application

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR8357M (en) * 1966-09-08 1971-02-08
WO1993023402A1 (en) * 1992-05-11 1993-11-25 Fujisawa Pharmaceutical Co., Ltd. 3-azetidinylthio-carbapeneme derivatives, their preparation and use as antimicrobial agents
JP2000191916A (en) * 1998-12-28 2000-07-11 Toshiba Corp Electroconductive composition, photosensitive resist, antistatic agent and production of semiconductor device
WO2002053158A1 (en) * 2000-12-29 2002-07-11 Alteon, Inc. Method for treating glaucoma ib
WO2003022812A1 (en) * 2001-09-12 2003-03-20 Solvent Innovation Gmbh Organic sulfates as ionic liquids
WO2004035542A1 (en) * 2002-10-13 2004-04-29 Solvent Innovation Gmbh Functionalised ionic liquids and method for the production thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR8357E (en) 1906-12-14 1908-02-28 "Paris-Ignicole" Gas incandescent burner
DE10105751B4 (en) * 2001-02-08 2005-09-29 Oxeno Olefinchemie Gmbh Process for the preparation of 1-octene

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR8357M (en) * 1966-09-08 1971-02-08
WO1993023402A1 (en) * 1992-05-11 1993-11-25 Fujisawa Pharmaceutical Co., Ltd. 3-azetidinylthio-carbapeneme derivatives, their preparation and use as antimicrobial agents
JP2000191916A (en) * 1998-12-28 2000-07-11 Toshiba Corp Electroconductive composition, photosensitive resist, antistatic agent and production of semiconductor device
WO2002053158A1 (en) * 2000-12-29 2002-07-11 Alteon, Inc. Method for treating glaucoma ib
WO2003022812A1 (en) * 2001-09-12 2003-03-20 Solvent Innovation Gmbh Organic sulfates as ionic liquids
WO2004035542A1 (en) * 2002-10-13 2004-04-29 Solvent Innovation Gmbh Functionalised ionic liquids and method for the production thereof

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
DATABASE BEILSTEIN BEILSTEIN INSTITUTE FOR ORGANIC CHEMISTRY, FRANKFURT-MAIN, DE; 1991, XP002308443, Database accession no. 4084291 (BRN) *
DATABASE BEILSTEIN BEILSTEIN INSTITUTE FOR ORGANIC CHEMISTRY, FRANKFURT-MAIN, DE; 1992, XP002308444, Database accession no. 5193589 (BRN) *
HERRMANN W A ET AL.: "Heterocyclic Carbenes. 18. Chiral Oxazoline/Imidazoline-2-ylidene Complexes", ORGANOMETALLICS., vol. 17, no. 11, 1998, USACS, COLUMBUS, OH., pages 2162 - 2168, XP002308440 *
SASAKI K ET AL: "A novel glycosidation of glycosyl fluoride using a designed ionic liquid and its effect on the stereoselectivity", TETRAHEDRON LETTERS., vol. 45, no. 38, 13 August 2004 (2004-08-13), NLELSEVIER SCIENCE PUBLISHERS, AMSTERDAM., pages 7043 - 7047, XP002308442 *
TETRAHEDRON, vol. 42, no. 2, 1986, pages 699 - 708 *
WASSERSCHEID P ET AL: "Ionic Liquids-New Solutions for Transition Metal Catalysis", ANGEWANDTE CHEMIE. INTERNATIONAL EDITION, VERLAG CHEMIE. WEINHEIM, DE, vol. 39, no. 21, 3 November 2000 (2000-11-03), pages 3773 - 3789, XP000967912, ISSN: 0570-0833 *
WASSERSCHEID P ET AL: "New, functionalised ionic liquids from Michael-type reactions - A chance for combinatorial ionic liquid development", CHEMICAL COMMUNICATIONS, no. 16, 3 July 2003 (2003-07-03), GBROYAL SOCIETY OF CHEMISTRY., pages 2038 - 2039, XP002308439 *
ZHAO D ET AL: "Synthesis and Characterization of Ionic Liquids Incorporating the Nitrile Functionality", INORGANIC CHEMISTRY, vol. 43, no. 6, 27 February 2004 (2004-02-27), USAMERICAN CHEMICAL SOCIETY, EASTON, pages 2197 - 2205, XP002308441 *

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7361678B2 (en) 2002-03-05 2008-04-22 Transtech Pharma, Inc. Azole derivatives and fused bicyclic azole derivatives as therapeutic agents
EP1721900A4 (en) * 2004-02-24 2009-10-28 Kanto Kagaku Novel imidazolium compound
US8609572B2 (en) 2005-01-04 2013-12-17 The Queen's University Of Belfast Basic ionic liquids
WO2006072775A3 (en) * 2005-01-04 2007-04-26 Univ Belfast Ionic liquids with a cation comprising a basic moiety
WO2007038360A3 (en) * 2005-09-22 2007-06-07 Du Pont Preparation of polytrimethylene ether glycol and copolymers thereof
US8395003B2 (en) 2007-04-26 2013-03-12 IFP Energies Nouvelles Metal nanoparticle-based catalytic composition that contains a nitrogen-containing ligand in an ionic liquid, process for preparation, process for hydrogenation of an olefinic feedstock
WO2008145836A3 (en) * 2007-04-26 2009-02-19 I F P Catalytic composition including metal nanoparticles containing a nitrogen ligand in an ionic liquid, method for preparing same and method for hydrogenating an olefinic load
FR2915406A1 (en) * 2007-04-26 2008-10-31 Inst Francais Du Petrole CATALYTIC COMPOSITION BASED ON NANOPARTICLES CONTAINING NITROGEN LIGAND IN IONIC LIQUID, PROCESS FOR PREPARING, METHOD FOR HYDROGENATION OF OLEFINIC CHARGE
US8580833B2 (en) 2009-09-30 2013-11-12 Transtech Pharma, Inc. Substituted imidazole derivatives and methods of use thereof
US9598375B2 (en) 2009-09-30 2017-03-21 Vtv Therapeutics Llc Substituted imidazole derivatives and methods of use thereof
US10363241B2 (en) 2009-09-30 2019-07-30 Vtv Therapeutics Llc Substituted imidazole derivatives and methods of use thereof
MD4233C1 (en) * 2012-03-02 2014-01-31 Институт Химии Академии Наук Молдовы Catalyst for the synthesis of 2-pyrrol-3-iloxindole derivatives
EP4002505A1 (en) 2020-11-13 2022-05-25 Toyota Jidosha Kabushiki Kaisha Functionalized ionic liquids as stabilizers for perovskite solar cells
CN115160267A (en) * 2022-08-04 2022-10-11 安阳工学院 An ionic liquid composite medium and method for preparing furfural compounds using the same
CN115160267B (en) * 2022-08-04 2024-01-16 安阳工学院 Ionic liquid type composite medium and method for preparing furfural compounds by adopting ionic liquid type composite medium

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