CN101138741A - Ionic liquid loaded ruthenium catalyst containing pyridine ligand and producing method thereof - Google Patents

Ionic liquid loaded ruthenium catalyst containing pyridine ligand and producing method thereof Download PDF

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CN101138741A
CN101138741A CNA2007100469902A CN200710046990A CN101138741A CN 101138741 A CN101138741 A CN 101138741A CN A2007100469902 A CNA2007100469902 A CN A2007100469902A CN 200710046990 A CN200710046990 A CN 200710046990A CN 101138741 A CN101138741 A CN 101138741A
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ionic liquid
pyridine ligand
catalyst
organic solvent
ion liquid
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谢美然
马卓
孔毅
韩会景
王伟珍
史佳鑫
李金欣
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East China Normal University
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Abstract

The present invention relates to a ruthenium catalyst and a preparation method of the catalyst, in particular relates to a pyridine ligand compring and ion liquid supported ruthenium catalyst and a preparation method of the catalyst, and belongs to the catalyst and catalyst preparation technical field. The imidazole ion liquid reacts with 4-hydroxypyridine to get the pyridine group comprising imidazole ion liquid, and the pyridine group comprising imidazole ion liquid coordinates with ruthenium to make the catalyst. As the ruthenium catalyst made comprises the ion liquid section, the catalyst can be well dissolved in a polar solvent, in particular an ion liquid, so as to realize the ring opening metathesis polymerization (ROMP) reaction in the pure ion liquid. The ruthenium eliminates the shortcoming that the prior ruthenium catalyst is provided with the bad solubility in the polar solvent. The catalyst can be dissolved in the polar solvent, like the alcohol, acetone and ion liquid, and further realizes the ring opening metathesis polymerization (ROMP) reaction in the pure ion liquid. Thus, the application scope of the ruthenium is expanded.

Description

A kind of ionic liquid loaded ruthenium catalyst and preparation thereof that contains pyridine ligand
Technical field
The present invention relates to a kind of ruthenium catalyst and preparation method thereof, particularly a kind of ionic liquid loaded ruthenium catalyst that contains pyridine ligand and preparation method thereof belongs to catalyst and preparing technical field thereof.
Background technology
Ruthenium catalyst is the key factor that influences monomer polymerization in the ring opening metathesis polymerization.The present existing Grubbs first generation and second generation catalyst be owing to have good stable and functional group's tolerance, can carry out living polymerization and obtain the clear and definite product of structure and become the catalyst of extensive use.But the Grubbs catalyst only has fine solubility in non-polar solvens such as carrene, benzene, toluene, dissolubility is very poor in polar solvent such as alcohols, water and ionic liquid, and has limited the carrying out of its ring-opening metathesis polymerization (ROMP) reaction in polar solvent.
Summary of the invention
The objective of the invention is to overcome present existing ruthenium catalyst poorly soluble shortcoming in polar solvent, improve its dissolubility in ionic liquid isopolarity solvent, thereby be implemented in the polymerisation in the pure ionic liquid environment.
The structural formula of a kind of ionic liquid loaded ruthenium catalyst that contains pyridine ligand of the present invention is as follows:
Figure A20071004699000041
In the above-mentioned formula, R 1Be BF 4 -, PF 6 -Or CF 3COO -R 2Be H or methyl (CH 3); N is from 2 to 12 natural number, and [Ru] is Grubbs first generation catalyst or Grubbs second generation catalyst.
Work as R 1Be BF 4 -, R 2Be H, [Ru] is the Grubbs first generation or Grubbs second generation catalyst, and during n=2, the described ionic liquid loaded ruthenium catalyst that contains pyridine ligand is:
Figure A20071004699000042
Work as R 1Be BF 4 -, R 2For-CH 3, [Ru] is the Grubbs first generation or Grubbs second generation catalyst, during n=2, the described ionic liquid loaded ruthenium catalyst that contains pyridine ligand is:
Figure A20071004699000043
Work as R 1Be PF 6 -, R 2Be H, [Ru] is the Grubbs first generation or Grubbs second generation catalyst, and during n=2, the described ionic liquid loaded ruthenium catalyst that contains pyridine ligand is:
Figure A20071004699000051
Work as R 1Be PF 6 -, R 2For-CH 3, [Ru] is the Grubbs first generation or Grubbs second generation catalyst, during n=2, the described ionic liquid loaded ruthenium catalyst that contains pyridine ligand is:
Figure A20071004699000052
Work as R 1Be CF 3COO -, R 2Be H, [Ru] is the Grubbs first generation or Grubbs second generation catalyst, and during n=2, the described ionic liquid loaded ruthenium catalyst that contains pyridine ligand is:
Figure A20071004699000053
Work as R 1Be CF 3COO -, R 2For-CH 3, [Ru] is the Grubbs first generation or Grubbs second generation catalyst, during n=2, the described ionic liquid loaded ruthenium catalyst that contains pyridine ligand is:
Figure A20071004699000054
A kind of preparation method who contains the ionic liquid loaded ruthenium catalyst of pyridine ligand of the present invention, synthetic route is:
Figure A20071004699000055
In the above-mentioned formula, X=Cl, Br, R 1Be BF 4 -, PF 6 -Or CF 3COO -, R 2Be H or methyl (CH 3), M tBe Na or K, n is from 2 to 12 natural number, and [Ru] is Grubbs first generation catalyst or Grubbs second generation catalyst.
A kind of preparation method who contains the ionic liquid loaded ruthenium catalyst of pyridine ligand of the present invention, specifically carry out according to following order, step:
The first step: the ionic liquid that the composite structure formula is following:
In the above-mentioned formula, R 1Be BF 4 -, PF 6 -Or CF 3COO -, R 2Be H or methyl (CH 3), n is from 2 to 12 natural number.
(1) with glyoxaline compound With halohydrin X-(CH 2) n-OH in organic solvent and under the nitrogen protection, in 60～120 ℃ of reactions 6～12 hours, generates ionic liquid according to mol ratio reaction in 1: 1～1: 1.2
Figure A20071004699000063
Described organic solvent is benzene or toluene, and its consumption is 5～8ml/g glyoxaline compound.
(2) ionic liquid of the middle gained of step (1) and salt are pressed 1: 1.2～1: 1.5 mol ratio, in water or organic solvent, and stirring at room, the reaction time is 12～48 hours.Through with the anion exchange of salt, obtain ionic liquid
Figure A20071004699000064
Used salt is NaBF 4, KPF 6Or CF 3COONa.Described organic solvent is acetone, ethanol, acetonitrile or DMF, and its consumption is 10～50ml/g ionic liquid.
(3) ionic liquid that obtains in the step (2) and paratoluensulfonyl chloride were by 1: 1～1: 1.2 mol ratio, and ice-water bath stirs down, and the reaction time is 4～12 hours, makes ion liquid p-methyl benzenesulfonic acid ester in organic solvent and alkaline reagent Described organic solvent is carrene or acetonitrile, and consumption is 6～12ml/g ionic liquid.Alkaline reagent is triethylamine or pyridine, and consumption is identical with paratoluensulfonyl chloride.The p-methyl benzenesulfonic acid ester that obtains reacts under the effect of alkali with the 4-pyridone again, obtains containing ion liquid pyridine ligand
Figure A20071004699000071
Second step: the synthetic ionic liquid loaded ruthenium catalyst that contains pyridine ligand:
With gained in 1 contain ion liquid pyridine ligand with [Ru] 5: 1 in molar ratio～10: 1, preferred molar ratio is 8: 1, reaction temperature is a room temperature, reaction time is 1～4 hour, makes ionic liquid loaded ruthenium catalyst that contains pyridine ligand and the mixture that contains ion liquid pyridine ligand in mixed organic solvents.Described mixed organic solvents is the mixed solvent of carrene or acetone and carrene, and preferred molar ratio is an acetone: carrene=1.2: 1.This reactant mixture drained solvent after the organic solvent purification process, obtain containing the ionic liquid loaded ruthenium catalyst of pyridine ligand
Figure A20071004699000072
Described organic solvent is carrene, acetone, n-hexane.
R in the above-mentioned formula 1Be BF 4 -, PF 6 -Or CF 3COO -, R 2Be H or methyl (CH 3), n is from 2 to 12 natural number, [Ru] is Grubbs first generation catalyst or Grubbs second generation catalyst.
In the method for the present invention, X represents halogen, preferred chlorine and bromine.
The ionic liquid loaded ruthenium catalyst that contains pyridine ligand of the present invention detects through magnetic nuclear resonance method, is confirmed that it is described ruthenium catalyst.
Beneficial effect: the ionic liquid loaded ruthenium catalyst that contains pyridine ligand of the present invention has improved existing ruthenium catalyst poorly soluble shortcoming in polar solvent, this catalyst can be dissolved in polar solvent such as alcohols, acetone and the ionic liquid, and then be implemented in ring opening metathesis polymerization in the pure ionic liquid, expanded the range of application of ruthenium catalyst.
The specific embodiment
Embodiment provided by the invention is as follows:
Embodiment 1
1,2-dimethyl-3-hydroxyethyl imidazole chlorion liquid (1) synthetic
Figure A20071004699000073
In the 250ml reaction bulb, add 1, the 2-methylimidazole (19.2g, 200mmol) and chlorethanol (16.1ml, 240mmol), with the dissolving of 20ml toluene, 110 ℃ of reactions 8 hours stop reaction, leave standstill, and go upper toluene.Again with toluene give a baby a bath on the third day after its birth time (20ml * 3).Add 20ml acetone in thick product, 70 ℃ of stirring 30min that reflux leave standstill, and remove the upper strata solvent.Repeat to wash secondary, leave standstill with acetone, cooling, lower floor has light yellow solid to separate out.Light yellow thick product is recrystallized with acetonitrile, obtains white crystal, vacuum drying obtains compound 1 (27.5g, productive rate 78%). 1H-NMR(D 2O，δ)：7.35(d，2H，N-CH＝HC-N)，4.22(t，2H，N-CH 2)，3.87(t，2H，CH 2-OH)，3.74(s，3H，N-CH 3)，2.56(s，3H，C-CH 3)； 13C-NMR(D 2O，δ)：146.36(N-C-N)，123.76，122.39(HC＝CH)，61.31(CH 2-OH)，51.53(N-CH 2)，36.12(N-CH 3)，10.53(C-CH 3)。
Embodiment 2
1,2-dimethyl-3-ethoxy hexafluorophosphate ionic liquid (2) synthetic
Figure A20071004699000081
With KPF 6(13.2g 72mmol) is dissolved in the 80ml water, and with the ice-water bath cooling, (10.6g, 50ml aqueous solution 60mmol) slowly splashes into compound 1 then.Rise to room temperature reaction 12 hours after dripping gradually, stop reaction.Slough aqueous solvent, obtain light yellow thick liquid (containing white solid).Use the 50ml acetone solution, filter, filtrate use anhydrous sodium sulfate drying, and taking off behind the solvent must colourless viscous liquid, and vacuum drying obtains compound 2 (14.2g, productive rate 83%). 1H-NMR(D 2O，δ)：7.40(d，2H，HC＝CH)，4.27(t，2H，N-CH 2)，3.94(t，2H，CH 2-OH)，3.80(s，3H，N-CH 3)，2.62(s，3H，C-CH 3)； 13C-NMR(D 2O，δ)：146.36(N-C-N)，123.76，122.39(HC＝CH)，61.31(CH 2-OH)，51.53(N-CH 2)，36.12(N-CH 3)，10.53(C-CH 3)； 31P-NMR(D 2O，δ)：-144.4(PF 6 -)。
Embodiment 3
1,2-dimethyl-3-ethyl p-toluenesulfonate hexafluorophosphate imidazole ion liquid (3) synthetic
Figure A20071004699000082
Under the nitrogen protection, (5.72g, 20mmol), with the dissolving of 35ml acetonitrile, (3.4ml, 24mmol), ice-water bath cools off to add triethylamine then to add 2 in 250ml Schlenk reaction bulb.(4.58g 24mmol) with the dissolving of 25mL acetonitrile, drips under the condition of ice bath paratoluensulfonyl chloride.After dripping, keep 0-5 ℃ of reaction 1 hour, rose to room temperature reaction again 10 hours, stop reaction.Filter, take off solvent, get solid and dark viscous fluid, use 100ml CH 2Cl 2Dissolving, after the washing repeatedly, the organic facies anhydrous Na 2SO 4Dry.Slough CH 2Cl 2Pale brown look solid, with solid acetone: ether=be recrystallized at 2: 1 light yellow solid, vacuum drying obtains product 4.84g, productive rate 55.5%. 1H-NMR(CO(CD 3) 2，δ)：7.76(2H，HC＝CHim)，7.57(2H，2×CH aryl-C-S)，7.51(2H，2×CH aryl-C-CH 3)，4.68(2H，N-CH 2)，4.53(2H，CH 2-O)，3.96(3H，N-CH 3)，2.76(3H，N-C-CH 3)，2.48(3H，C aryl-CH 3)； 13C-NMR(CO(CD 3) 2，δ)：146.65(C aryl-CH 3)，146.49(C 2im)，133.33(C aryl-S)，131.11(2×CH aryl-C aryl-CH 3)，128.62(2×CH aryl-C aryl-S)，123.75(C 4im)，122.31(C 5im)，69.01(CH 2-O)，48.00(N-CH 2)，35.70(N-CH 3)，21.54(C aryl-CH 3)，9.91(C-CH 3)。
Embodiment 4
1,2-dimethyl-3-ethoxy pyridine hexafluorophosphate imidazole ion liquid (4) synthetic
Figure A20071004699000091
Under the nitrogen protection, in 100ml Schlenk reaction bulb, add the 4-pyridone (0.58g, 6.05mmol) and potash (1.25g 9.08mmol), with 20ml DMF dissolving, is warming up to 80 ℃ and reacted 5 hours.(80 ℃ are stirred 4d, stop reaction for 2.20g, DMF 5.00mmol) (10ml) solution, and system is a sepia to drip 3 then.Cold filtration except that desolvating, adds 30ml acetone and stirs, and removes by filter insoluble matter, sloughs acetone, residue brown solid acetone: ethyl acetate=1: 1 recrystallization, get light yellow crystal, and vacuum drying obtains product 0.78g, productive rate 43%. 1H-NMR(CO(CD 3) 2，δ)：8.40(2H，2×CH Py-N)，7.75-7.63(2H，CH＝CHim)，6.95(2H，2×CH Py-C-O)，4.83(2H，N-CH 2)，4.57(2H，CH 2-O)，3.97(3H，N-CH 3))，2.95(3H，N-C-CH 3)； 13C-NMR：(CO(CD 3) 2，δ)：165.46(C Py-O)，152.63(2×CH Py-N)，147.63(C 2im)，124.20(C 4im)，123.21(C 5im)，111.71(2×CH Py-C-O)，67.62(CH 2-O)，49.02(N-CH 2)，36.27(N-CH 3)，10.70(C-CH 3)；EA(％)：C39.73，H4.61，N11.73(calc：C39.68，H4.44，N11.57)。
Embodiment 5
Synthetic (5) that contain the ionic liquid loaded ruthenium catalyst of pyridine ligand
Figure A20071004699000092
Under the high purity nitrogen protection, (145mg, 0.40mmol), (44.2mg, 0.050mmol), two pipes are vacuum nitrogen filling gas respectively, replaces three times to add second generation Grubbs catalyst in another arm to add part 4 in 10mL Schlenk pipe.With the acetone solution part 4 of the dry deoxidation of 1.2ml, with the CH of 1ml drying 2Cl 2Catalyst-solvent, two by-reaction pipes are added drop-wise to catalyst solution in the ligand solution under nitrogen atmosphere after liquid nitrogen frozen-vacuumize-inflated with nitrogen-thawing.Normal temperature stirs down, and system becomes blackish green by rufous gradually, reacts 4 hours, stops reaction.Solvent is taken off in nitrogen protection decompression down, gets green solid.Add 1ml CH 2Cl 2, solution is yellow green, and insoluble solids is green, leaves standstill, and the sucking-off supernatant liquor is abandoned it.Remaining solid is used a little CH respectively 2Cl 2With hexane wash once, drying under reduced pressure gets green solid (this solid is part 4 and mixture of catalysts). 1H-NMR (CO (CD 3) 2, δ): 16.27 (1H, Ru=CH-Ph), 9.36 (1H, CH-Ru), 7.97～8.11 (CH Py), 7.73～7.62 (CHim=CHim), 7.43～7.35 (CH Aryl), 6.5 (CH Py), 5.94～5.91 (CH 2), 5.54～5.51 (CH 2), 4.80 (CH 2), 4.54 (CH 2), 4.00 (N-CH 3), 2.97 (C-CH 3), 2.88～2.71 (CH 3); 13C-NMR:(CO (CD 3) 2, δ): 212.64 (N-CH-Ru), 165.01 (C Py-O), 152.11 (2 * CH Py-N), 146.63 (C 2Im), 141.64,138.57,130.35,129.94,128.87,124.39 (C 4Im), 124.11,123.59,123.46,122.53 (C 5Im), 118.57,111.34 (2 * CH Py-C-O), 110.92,69.27,67.17 (CH 2-O), 54.91,48.31 (N-CH 2), 35.65 (N-CH 3), 20.21,18.85,10.85 (C-CH 3), 10.08; 31P-NMR (CO (CD 3) 2, δ) :-143.3 (PF 6 -); ICP: the content of catalyst is 14wt%.
Embodiment 6
1,2-dimethyl-3-dodecyl alcohol imidazoles bromide ion liquid (6) synthetic
Figure A20071004699000101
Add 1 in the 250ml reaction bulb, (9.6g, 100mmol) (29.2g, 110mmol), with the dissolving of 40ml toluene, 70 ℃ were reacted 8 hours the 2-methylimidazole, stopped reaction, left standstill, and went upper toluene with 12-bromo lauryl alcohol.Again with toluene give a baby a bath on the third day after its birth time (30ml * 3).Add 40ml acetone in thick product, 70 ℃ of stirring 30min that reflux leave standstill, and remove the upper strata solvent.Repeat to wash secondary, leave standstill with acetone, cooling, lower floor has light yellow solid to separate out.Light yellow thick product is recrystallized with acetonitrile, obtains white crystal, vacuum drying obtains compound 6 (32.2g, productive rate 89%). 1H-NMR(D 2O，δ)：7.35(d，2H，N-CH＝HC-N)，4.04(t，2H，N-CH 2)，3.50(t，2H，CH 2-OH)，3.74(s，3H，N-CH 3)，2.56(s，3H，C-CH 3)，1.74(t，2H，N-CH 2-CH 2)，1.53(t，2H，CH 2-CH 2-OH)，1.43(t，2H，CH 2-(CH 2) 2-OH)，1.29(m，12H，N-(CH 2) 2-CH 2)； 13C-NMR(D 2O，δ)：146.36(N-C-N)，123.76，122.39(HC＝CH)，61.31(CH 2-OH)，51.53(N-CH 2)，36.12(N-CH 3)，32.2(CH 2-CH 2-OH)，30.4(N-CH 2-CH 2)，27.1(N-(CH 2) 2-CH 2)，29.3(N-(CH 2) 3-CH 2)，25.6(CH 2-(CH 2) 2-OH))，10.53(C-CH 3)。
Embodiment 7
1,2-dimethyl-3-dodecyl alcohol hexafluorophosphate ionic liquid (7) synthetic
Figure A20071004699000102
With KPF 6(13.2g 72mmol) is dissolved in the 80ml water, and with the ice-water bath cooling, (13.2g, 150ml aqueous solution 60mmol) slowly splashes into compound 6 then.Rise to room temperature reaction 48 hours after dripping gradually, stop reaction.Slough aqueous solvent, obtain white solid.Use 50ml CH 2Cl 2Dissolving is filtered, filtrate water washing (30ml * 4), and the organic facies anhydrous sodium sulfate drying, taking off behind the solvent must white solid, and vacuum drying obtains compound 7 (21.2g, productive rate 83%). 1H-NMR(DMSO，δ)：7.35(d，2H，N-CH＝HC-N)，4.04(t，2H，N-CH 2)，3.50(t，2H，CH 2-OH)，3.74(s，3H，N-CH 3)，2.56(s，3H，C-CH 3)，1.74(t，2H，N-CH 2-CH 2)，1.53(t，2H，CH 2-CH 2-OH)，1.43(t，2H，CH 2-(CH 2) 2-OH)，1.29(m，12H，N-(CH 2) 2-CH 2)； 13C-NMR(DMSO，δ)：146.36(N-C-N)，123.76，122.39(HC＝CH)，61.31(CH 2-OH)，51.53(N-CH 2)，36.12(N-CH 3)，32.2(CH 2-CH 2-OH，30.4(N-CH 2-CH 2)，27.1(N-(CH 2) 2-CH 2)，29.3(N-(CH 2) 3-CH 2)，25.6(CH 2-(CH 2) 2-OH))，10.53(C-CH 3)。
Embodiment 8
1,2-dimethyl-3-p-methyl benzenesulfonic acid dodecyl ester hexafluorophosphate imidazole ion liquid (8) synthetic
Figure A20071004699000111
Under the nitrogen protection, (8.53g, 20mmol), with the dissolving of 35ml acetonitrile, (3.4ml, 24mmol), ice-water bath cools off to add triethylamine then to add 7 in 250ml Schlenk reaction bulb.(4.58g 24mmol) with the dissolving of 25mL acetonitrile, drips under the condition of ice bath paratoluensulfonyl chloride.After dripping, keep 0-5 ℃ of reaction 1 hour, rose to room temperature reaction again 24 hours, stop reaction.Filter, take off solvent, get solid and dark viscous fluid, use 100ml CH 2Cl 2Dissolving, after the washing repeatedly, the organic facies anhydrous Na 2SO 4Dry.Slough CH 2Cl 2Pale brown look solid, with solid acetone: ether=be recrystallized at 2: 1 light yellow solid, vacuum drying obtains product 6.40g, productive rate 55.5%. 1H-NMR(DMSO，δ)：7.35(N-CH＝HC-N)，7.17(2×CH aryl-C-S)，7.11(2×CH aryl-C-CH 3)，4.04(N-CH 2)，3.50(CH 2-OH)，3.74(3H，N-CH 3)，2.56(3H，C-CH 3)，2.34(3H，C aryl-CH 3)，1.74(2H，N-CH 2-CH 2)，1.53(2H，CH 2-CH 2-OH)，1.43(2H，CH 2-(CH 2) 2-OH)，1.29(12H，N-(CH 2) 2-CH 2)； 13C-NMR(DMSO，δ)：146.65(C aryl-CH 3)，146.36(N-C-N)，135.33(C aryl-S)，131.11(2×CH aryl-C aryl-CH 3)，128.62(2×C Haryl-C aryl-S)，123.76，122.39(HC＝CH)，61.31(CH 2-OH)，51.53(N-CH 2)，36.12(N-CH 3)，32.2(CH 2-CH 2-OH)，30.4(N-CH 2-CH 2)，27.1(N-(CH 2) 2-CH 2)，29.3(N-(CH 2) 3-CH 2)，25.6(CH 2-(CH 2)2-OH)，21.34(C aryl-CH 3)，10.53(C-CH 3)。
Embodiment 9
1,2-dimethyl-3-dodecyloxy pyridine hexafluorophosphate imidazole ion liquid (9) synthetic
Figure A20071004699000112
Under the nitrogen protection, in 100ml Schlenk reaction bulb, add the 4-pyridone (0.58g, 6.05mmol) and potash (1.25g 9.08mmol), with 20ml DMF dissolving, is warming up to 80 ℃ and reacted 5 hours.(80 ℃ are stirred 4d, stop reaction for 2.91g, DMF 5.00mmol) (10ml) solution, and system is a sepia to drip 8 then.Cold filtration except that desolvating, adds 30ml acetone and stirs, and removes by filter insoluble matter, sloughs acetone, residue brown solid acetone: ethyl acetate=1: 1 recrystallization, get light yellow crystal, and vacuum drying obtains product 1.07g, productive rate 43%. 1H-NMR(DMSO，δ)：8.25(2H，2×CH Py-N)，7.35(2H，N-CH＝HC-N)，6.85(2H，2×CH Py-C-O)，4.04(2H，N-CH 2)，3.50(2H，CH 2-OH)，3.74(3H，N-CH 3)，2.56(3H，C-CH 3)，1.74(2H，N-CH 2-CH 2)，1.53(2H，CH 2-CH 2-OH)，1.43(2H，CH 2-(CH 2) 2-OH)，1.29(12H，N-(CH 2) 2-CH 2)； 13C-NMR(DMSO，δ)：156.2(C Py-O)，150.7(2×CH Py-N)，146.36(N-C-N)，123.76，122.39(HC＝CH)，100.71(2×CH Py-C-O)，61.31(CH 2-OH)，51.53(N-CH 2)，36.12(N-CH 3)，32.2(CH 2-CH 2-OH)，30.4(N-CH 2-CH 2)，27.1(N-(CH 2) 2-CH 2)，29.3(N-(CH 2) 3-CH 2)，25.6(CH 2-(CH 2) 2-OH)，10.53(C-CH 3)。
Embodiment 10
Synthetic (10) that contain the ionic liquid loaded ruthenium catalyst of pyridine ligand
Figure A20071004699000121
Under the high purity nitrogen protection, (200mg, 0.40mmol), (44.2mg, 0.050mmol), two pipes are vacuum nitrogen filling gas respectively, replaces three times to add second generation Grubbs catalyst in another arm to add part 9 in 10ml Schlenk pipe.With the acetone solution part 9 of the dry deoxidation of 1.2ml, with the CH of 1ml drying 2Cl 2Catalyst-solvent, two by-reaction pipes are added drop-wise to catalyst solution in the ligand solution under nitrogen atmosphere after liquid nitrogen frozen-vacuumize-inflated with nitrogen-thawing.Normal temperature stirs down, and system becomes blackish green by rufous gradually, reacts 4 hours, stops reaction.Solvent is taken off in nitrogen protection decompression down, gets green solid.Add 1ml CH 2Cl 2, solution is yellow green, and insoluble solids is green, leaves standstill, and the sucking-off supernatant liquor is abandoned it.Remaining solid is used a little CH respectively 2Cl 2With hexane wash once, drying under reduced pressure gets green solid (this solid is part 9 and mixture of catalysts). 1H-NMR(DMSO，δ)：16.27(1H，Ru＝CH-Ph)，9.43(1H，CH-Ru)，7.73～7.62(CHim＝CHim)，7.97～8.25(CH Py)，7.43～7.35(CH aryl)，6.85(CH Py)，4.04(N-CH 2)，3.50(CH 2-OH)，3.94(N-CH 3)，2.88～2.71(CH 3)，2.56(3H，C-CH 3)，1.74(N-CH 2-CH 2)，1.53(CH 2-CH 2-OH)，1.43(CH 2-(CH 2) 2-OH)，1.29(N-(CH 2) 2-CH 2)； 13C-NMR(DMSO，δ)：212.64(N-CH-Ru)，165.7(C Py-O)，146.36(N-C-N)，150.11(2×CH Py-N)，123.76，122.39(HC＝CH)，100.74(2×CH Py-C-O)，61.31(CH 2-OH)，51.53(N-CH 2)，36.12(N-CH 3)，32.2(CH 2-CH 2-OH)，30.4(N-CH 2-CH 2)，27.1(N-(CH 2) 2-CH 2)，29.3(N-(CH 2) 3-CH 2)，25.6(CH 2-(CH 2) 2-OH)，10.53(C-CH 3)。 31P-NMR(CO(CD 3) 2，δ)：-143.3(PF 6 -)。

Claims (5)

1. ionic liquid loaded ruthenium catalyst that contains pyridine ligand is characterized in that structural formula is as follows:
Figure A2007100469900002C1
R in the formula 1Be BF 4 -, PF 6 -Or CF 3COO -R 2Be H or methyl; N is from 2 to 12 natural number; [Ru] is Grubbs first generation catalyst or Grubbs second generation catalyst.
2. preparation method who contains the ionic liquid loaded ruthenium catalyst of pyridine ligand is characterized in that may further comprise the steps:
The first step: the composite structure formula is following contains ion liquid pyridine ligand:
R in the formula 1Be BF 4 -, PF 6 -Or CF 3COO -, R 2Be H or methyl, n is from 2 to 12 natural number;
Second step: the synthetic ionic liquid loaded ruthenium catalyst that contains pyridine ligand:
With containing of gained in the first step ion liquid pyridine ligand with [Ru] 5: 1 in molar ratio～10: 1 in mixed organic solvents, mixed organic solvents is the mixed solvent of acetone and carrene, mol ratio is an acetone: carrene=1.2: 1; Make ionic liquid loaded ruthenium catalyst that contains pyridine ligand and the mixture that contains ion liquid pyridine ligand,, obtain containing the ionic liquid loaded ruthenium catalyst of pyridine ligand through the organic solvent purification process.
3. the preparation method who contains the ionic liquid loaded ruthenium catalyst of pyridine ligand as claimed in claim 2, it is characterized in that containing ion liquid pyridine ligand is 8: 1 with [Ru] in molar ratio.
4. the preparation method who contains the ionic liquid loaded ruthenium catalyst of pyridine ligand as claimed in claim 2 is characterized in that the organic solvent that purifying is used is carrene, acetone or n-hexane.
5. the preparation method who contains the ionic liquid loaded ruthenium catalyst of pyridine ligand as claimed in claim 2 is characterized in that the first step contains the synthetic of ion liquid pyridine ligand and comprises the steps:
(1) with glyoxaline compound
Figure A2007100469900003C1
With halohydrin X-(CH 2) n-OH was according to 1: 1～1: 1.2 mol ratio, and reaction generates ionic liquid in organic solvent and under the nitrogen protection
Figure A2007100469900003C2
Wherein organic solvent is benzene or toluene, and X represents halogen;
(2) mol ratio that the ionic liquid and the salt of gained in (1) are pressed 1: 1.2～1: 1.5 is reacted in water or organic solvent, generates ionic liquid
Figure A2007100469900003C3
Used salt is NaBF 4, KPF 6Or CF 3COONa; Organic solvent is acetone, ethanol, acetonitrile or DMF;
(3) ionic liquid and the paratoluensulfonyl chloride of gained in (2) are pressed 1: 1～1: 1.2 mol ratio, ice-water bath (0～5 ℃) stirs down, makes ion liquid p-methyl benzenesulfonic acid ester in organic solvent and alkaline reagent
Figure A2007100469900003C4
Organic solvent is carrene, acetonitrile; Alkaline reagent is triethylamine or pyridine, and consumption is identical with paratoluensulfonyl chloride;
(4) with 4-pyridone and K 2CO 3By 1: 1.5～1: 3 mol ratio, reaction temperature was 60～80 ℃, reacts in organic solvent, makes phenol potassium; The ion liquid p-methyl benzenesulfonic acid ester of gained in (3) is splashed in the phenol potassium solution, and reaction temperature is 60～80 ℃, obtains containing ion liquid pyridine ligand; Reaction finishes the back to be handled with organic solvent, obtains the colourless crystallization product
Figure A2007100469900003C5
Organic solvent is an acetonitrile, DMF, acetone or ethyl acetate;
(5) gained in (4) is contained ion liquid pyridine ligand and [Ru] 5: 1 in molar ratio～10: 1, reaction temperature is a room temperature, and the reaction time is 1～4 hour, makes the ionic liquid loaded ruthenium catalyst that contains pyridine ligand in organic solvent
Figure A2007100469900003C6
Described organic solvent is the mixed solvent (1.2: 1) of carrene or acetone and carrene.
CNA2007100469902A 2007-10-12 2007-10-12 Ionic liquid loaded ruthenium catalyst containing pyridine ligand and producing method thereof Pending CN101138741A (en)

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Publication number Priority date Publication date Assignee Title
CN101961661B (en) * 2009-07-22 2012-08-08 中国石油天然气股份有限公司 Organic metal catalyst for preparing cyclohexene by benzene hydrogenation and preparation method and application thereof
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JP2016003182A (en) * 2014-06-13 2016-01-12 トヨタ紡織株式会社 New ionic liquid, and method and apparatus for absorbing gas
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