CN101138741A - A kind of ruthenium catalyst supported by ionic liquid containing pyridine ligand and its preparation - Google Patents

Abstract

The invention relates to a ruthenium catalyst and a preparation method thereof, in particular to a ruthenium catalyst supported by an ionic liquid containing a pyridine ligand and a preparation method thereof, belonging to the technical field of catalyst and preparation thereof. The imidazole ionic liquid is reacted with 4-hydroxypyridine to obtain the imidazole ionic liquid containing pyridine group and coordinated with [Ru]. The prepared ruthenium catalyst can be well dissolved in a polar solvent, especially an ionic liquid, because it contains an ionic liquid part, thereby realizing a ring-opening metathesis polymerization (ROMP) reaction in a pure ionic liquid. The ruthenium catalyst improves the disadvantage of poor solubility in polar solvents of existing ruthenium catalysts, and the catalyst can be dissolved in polar solvents such as alcohols, acetone, and ionic liquids, thereby realizing ring-opening metathesis in pure ionic liquids The polymerization reaction expands the application scope of ruthenium catalyst.

Description

A kind of ruthenium catalyst supported by ionic liquid containing pyridine ligand and its preparation

technical field

The invention relates to a ruthenium catalyst and a preparation method thereof, in particular to a ruthenium catalyst supported by an ionic liquid containing a pyridine ligand and a preparation method thereof, belonging to the technical field of catalyst and preparation thereof.

Background technique

Ruthenium catalyst is an important factor affecting monomer polymerization in ring-opening metathesis polymerization. The existing Grubbs first-generation and second-generation catalysts have become widely used catalysts due to their good stability and functional group tolerance, which can carry out living polymerization and obtain products with well-defined structures. But the Grubbs catalyst only has good solubility in nonpolar solvents such as methylene chloride, benzene, toluene, and has poor solubility in polar solvents such as alcohols, water and ionic liquids, and limits its use in polar solvents. in the ring-opening metathesis polymerization (ROMP) reaction.

Contents of the invention

The purpose of the present invention is to overcome the disadvantages of poor solubility of existing ruthenium catalysts in polar solvents, improve their solubility in polar solvents such as ionic liquids, so as to realize the polymerization reaction in a pure ionic liquid environment.

The structural formula of the ruthenium catalyst supported by a kind of ionic liquid containing pyridine ligand of the present invention is as follows:

In the above formula, R ₁ is BF ₄ ^- , PF ₆ ^- or CF ₃ COO ^- ; R ₂ is H or methyl (-CH ₃ ); n is a natural number from 2 to 12, [Ru] is the first generation of Grubbs Catalyst or Grubbs second generation catalyst.

When R ₁ is BF ₄ ⁻ , R ₂ is H, [Ru] is Grubbs first-generation or Grubbs second-generation catalyst, and n=2, the ruthenium catalyst supported by an ionic liquid containing a pyridine ligand is:

When R ₁ is BF ₄ ^- , R ₂ is -CH ₃ , [Ru] is Grubbs first-generation or Grubbs second-generation catalyst, and n=2, the ruthenium catalyst supported by an ionic liquid containing a pyridine ligand is :

When R ₁ is PF ₆ ⁻ , R ₂ is H, [Ru] is Grubbs first-generation or Grubbs second-generation catalyst, and n=2, the ruthenium catalyst supported by an ionic liquid containing a pyridine ligand is:

When R ₁ is PF ₆ ^- , R ₂ is -CH ₃ , [Ru] is Grubbs first-generation or Grubbs second-generation catalyst, and n=2, the ruthenium catalyst supported by an ionic liquid containing a pyridine ligand is :

When R ₁ is CF ₃ COO ^- , R ₂ is H, [Ru] is Grubbs first-generation or Grubbs second-generation catalyst, and n=2, the ruthenium catalyst supported by an ionic liquid containing a pyridine ligand is:

When R ₁ is CF ₃ COO ^- , R ₂ is -CH ₃ , [Ru] is Grubbs first-generation or Grubbs second-generation catalyst, n=2, the ruthenium catalyst supported by ionic liquid containing pyridine ligand for:

A kind of preparation method of the ruthenium catalyst supported by the ionic liquid containing pyridine ligand of the present invention, synthetic route is:

In the above formula, X=Cl, Br, R ₁ is BF ₄ ^- , PF ₆ ^- or CF ₃ COO ^- , R ₂ is H or methyl (-CH ₃ ), M _t is Na or K, n is from 2 Natural numbers to 12, [Ru] is Grubbs first-generation catalyst or Grubbs second-generation catalyst.

A kind of preparation method of the ruthenium catalyst supported by the ionic liquid containing pyridine ligand of the present invention, specifically carry out according to following order, step:

Step 1: Synthesize an ionic liquid with the following structural formula:

In the above formula, R ₁ is BF ₄ ^- , PF ₆ ^- or CF ₃ COO ^- , R ₂ is H or methyl (-CH ₃ ), and n is a natural number from 2 to 12.

所述有机溶剂为苯或甲苯，其用量为5～8ml/g咪唑类化合物。(1) the imidazole compound React with haloalcohol X-(CH ₂ ) _n -OH at a molar ratio of 1:1 to 1:1.2, in an organic solvent and under the protection of nitrogen, and react at 60-120°C for 6-12 hours to generate an ionic liquid

The organic solvent is benzene or toluene, and its dosage is 5-8ml/g imidazole compound.

所用盐为NaBF₄，KPF₆或CF₃COONa。所述有机溶剂为丙酮、乙醇、乙腈或DMF，其用量为10～50ml/g离子液体。(2) The ionic liquid obtained in step (1) and the salt are stirred in an aqueous phase or an organic solvent at room temperature in a molar ratio of 1:1.2 to 1:1.5, and the reaction time is 12 to 48 hours. After anion exchange with salt, the ionic liquid is obtained

The salts used were NaBF ₄ , KPF ₆ or CF ₃ COONa. The organic solvent is acetone, ethanol, acetonitrile or DMF, and its dosage is 10-50ml/g ionic liquid.

(3) The ionic liquid obtained in the step (2) and p-toluenesulfonyl chloride are in a molar ratio of 1:1 to 1:1.2, stirred under an ice-water bath, and the reaction time is 4 to 12 hours, prepared in an organic solvent and an alkaline reagent p-toluenesulfonate The organic solvent is dichloromethane or acetonitrile, and the dosage is 6-12ml/g ionic liquid. The basic reagent is triethylamine or pyridine, and the dosage is the same as that of p-toluenesulfonyl chloride. The obtained p-toluenesulfonate is then reacted with 4-hydroxypyridine under the action of a base to obtain a pyridine ligand containing an ionic liquid

The second step: synthesis of ruthenium catalyst supported by ionic liquid containing pyridine ligand:

所述有机溶剂为二氯甲烷、丙酮、正己烷。The pyridine ligand containing the ionic liquid obtained in 1 is mixed with [Ru] in a molar ratio of 5:1 to 10:1, preferably a molar ratio of 8:1, the reaction temperature is room temperature, and the reaction time is 1 to 4 hours. A mixture of the ruthenium catalyst supported by the ionic liquid containing the pyridine ligand and the pyridine ligand containing the ionic liquid is prepared in a mixed organic solvent. The mixed organic solvent is dichloromethane or a mixed solvent of acetone and dichloromethane, and the preferred molar ratio is acetone:dichloromethane=1.2:1. After the reaction mixture is drained of the solvent, it is purified by an organic solvent to obtain a ruthenium catalyst supported by an ionic liquid containing a pyridine ligand

Described organic solvent is dichloromethane, acetone, n-hexane.

In the above formula, R ₁ is BF ₄ ^- , PF ₆ ^- or CF ₃ COO ^- , R ₂ is H or methyl (-CH ₃ ), n is a natural number from 2 to 12, [Ru] is Grubbs first-generation catalyst Or Grubbs second-generation catalyst.

In the process of the present invention, X represents halogen, preferably chlorine and bromine.

The ruthenium catalyst supported by the ionic liquid containing the pyridine ligand of the present invention is detected by the nuclear magnetic resonance method, and it is confirmed that it is the ruthenium catalyst.

Beneficial effect: the ruthenium catalyst supported by ionic liquid containing pyridine ligand of the present invention improves the disadvantage of poor solubility of existing ruthenium catalysts in polar solvents, and this catalyst can be dissolved in polar solvents such as alcohols, acetone and ionic liquids In this way, the ring-opening metathesis polymerization reaction in pure ionic liquids is realized, which expands the application range of ruthenium catalysts.

Detailed ways

Embodiments provided by the invention are as follows:

Example 1

Synthesis of 1,2-Dimethyl-3-hydroxyethylimidazolium Chloride Ionic Liquid (1)

Add 1,2-dimethylimidazole (19.2g, 200mmol) and chloroethanol (16.1ml, 240mmol) into a 250ml reaction flask, dissolve in 20ml of toluene, react at 110°C for 8 hours, stop the reaction, let it stand, and pour off the upper layer toluene. Then wash three times with toluene (20ml×3). Add 20ml of acetone to the crude product, stir at reflux at 70°C for 30min, let stand, and pour off the upper solvent. Repeat washing with acetone twice, let it stand, and cool down, and a light yellow solid is precipitated in the lower layer. The light yellow crude product was recrystallized from acetonitrile to obtain white crystals, which were dried in vacuo to obtain compound 1 (27.5 g, yield 78%). ¹ H-NMR (D ₂ O, 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 ); ¹³ C-NMR (D ₂ O, δ): 146.36 (NCN), 123.76, 122.39 (HC=CH) , 61.31 (CH2 _- OH), 51.53 (N- _CH2 ), 36.12 (N- _CH3 ), 10.53 (C- _CH3 ).

Example 2

Synthesis of 1,2-Dimethyl-3-hydroxyethylhexafluorophosphate Ionic Liquid (2)

KPF ₆ (13.2g, 72mmol) was dissolved in 80ml of water, cooled with an ice-water bath, and then a 50ml aqueous solution of compound 1 (10.6g, 60mmol) was slowly dropped into it. After the dropwise addition, the reaction was gradually raised to room temperature for 12 hours, and the reaction was stopped. The solvent water was removed to obtain a light yellow viscous liquid (containing white solid). Dissolved with 50ml of acetone, filtered, and the filtrate was dried with anhydrous sodium sulfate, and the solvent was removed to obtain a colorless viscous liquid, which was dried in vacuo to obtain compound 2 (14.2g, yield 83%). ¹ H-NMR (D ₂ O, 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 ); ¹³ C-NMR (D ₂ O, δ): 146.36 (NCN), 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 ); ³¹ P-NMR (D ₂ O, δ): -144.4 (PF ₆ ^- ).

Example 3

Synthesis of 1,2-dimethyl-3-ethyl p-toluenesulfonate imidazolium ionic liquid (3)

Under nitrogen protection, 2 (5.72g, 20mmol) was added to a 250ml Schlenk reaction flask, dissolved in 35ml of acetonitrile, then triethylamine (3.4ml, 24mmol) was added, cooled in an ice-water bath. p-Toluenesulfonyl chloride (4.58g, 24mmol) was dissolved in 25mL of acetonitrile and added dropwise under ice-bath conditions. After the dropwise addition, the reaction was maintained at 0-5°C for 1 hour, then raised to room temperature for 10 hours, and the reaction was stopped. Filter and remove the solvent to obtain solid and dark viscous liquid, which are dissolved in 100ml CH ₂ Cl ₂ and washed with water several times, and the organic phase is dried with anhydrous Na ₂ SO ₄ . The CH ₂ Cl ₂ was removed to obtain a brown-yellow solid, which was recrystallized from acetone:ether=2:1 to obtain a light-yellow solid, which was dried in vacuo to obtain 4.84 g of the product, with a yield of 55.5%. ¹ H-NMR (CO(CD ₃ ) ₂ , δ): 7.76 (2H, HC=CHim), 7.57 (2H, 2×CH _aryl -CS), 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, NC-CH ₃ ), 2.48(3H, _Caryl -CH ₃ ); ¹³ C-NMR (CO(CD ₃ ) ₂ , δ): 146.65 (C _aryl -CH ₃ ), 146.49 (C ₂ im), 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 ₄ im), 122.31 (C ₅ im), 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 ).

Example 4

Synthesis of 1,2-Dimethyl-3-ethoxypyridine Hexafluorophosphate Imidazolium Ionic Liquid (4)

Under nitrogen protection, 4-hydroxypyridine (0.58g, 6.05mmol) and potassium carbonate (1.25g, 9.08mmol) were added into a 100ml Schlenk reaction flask, dissolved in 20ml DMF, and heated to 80°C for 5 hours. Then a DMF (10ml) solution of 3 (2.20g, 5.00mmol) was added dropwise, stirred at 80°C for 4d, the reaction was stopped, and the system was brown. Cool and filter, remove the solvent, add 30ml of acetone and stir, filter to remove insoluble matter, remove the acetone, and recrystallize the remaining brown solid with acetone:ethyl acetate=1:1 to obtain light yellow crystals, which are dried in vacuo to obtain 0.78g of the product. 43%. ¹ H-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 -CO), 4.83 (2H, N-CH ₂ ), 4.57 (2H, CH ₂ -O), 3.97 (3H, N-CH ₃ )), 2.95 (3H, NC-CH ₃ ); ¹³ C-NMR: (CO(CD ₃ ) ₂ , δ): 165.46 (C _Py -O), 152.63 (2×CH _Py -N), 147.63 (C ₂ im), 124.20 (C ₄ im), 123.21 (C ₅ im), 111.71 (2× CH _Py -CO), 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).

Example 5

Synthesis of Ruthenium Catalysts Supported by Ionic Liquids Containing Pyridine Ligands(5)

Under the protection of high-purity nitrogen, ligand 4 (145 mg, 0.40 mmol) was added to a 10 mL Schlenk tube, and the second-generation Grubbs catalyst (44.2 mg, 0.050 mmol) was added to another tube. three times. Dissolve the ligand 4 with 1.2ml of dry deoxygenated acetone, dissolve the catalyst with 1ml of dry CH ₂ Cl ₂ , freeze the two reaction tubes with liquid nitrogen-vacuumize-fill with nitrogen-thaw, add the catalyst solution dropwise under nitrogen atmosphere into the ligand solution. Stirring at room temperature, the system gradually changed from reddish brown to dark green, reacted for 4 hours, and stopped the reaction. Under nitrogen protection, the solvent was removed under reduced pressure to obtain a green solid. Add 1ml CH ₂ Cl ₂ , the solution is yellow-green, and the insoluble solid is green, let stand, suck out the supernatant, and discard it. The remaining solid was washed once with a little CH ₂ Cl ₂ and hexane, and dried under reduced pressure to obtain a green solid (the solid is a mixture of ligand 4 and catalyst). ¹ H-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 ); ¹³ C-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 ₂ im), 141.64, 138.57, 130.35, 129.94, 128.87, 124.39 (C ₄ im), 124.11, 123.59, 123.46, 122.53 (C ₅ im), 118.57, 111.34 (2×CH _Py -CO), 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; ³¹ P-NMR (CO(CD ₃ ) ₂ , δ): -143.3 (PF ₆ ^- ); ICP: The catalyst content is 14 wt%.

Example 6

Synthesis of 1,2-Dimethyl-3-dodecyl imidazolium bromide ionic liquid (6)

Add 1,2-dimethylimidazole (9.6g, 100mmol) and 12-bromododecanol (29.2g, 110mmol) into the 250ml reaction flask, dissolve with 40ml toluene, react at 70°C for 8 hours, stop the reaction, and Set aside, pour off the upper layer of toluene. Then wash three times with toluene (30ml×3). Add 40ml of acetone to the crude product, stir at reflux at 70°C for 30min, let stand, and pour off the upper solvent. Repeat washing with acetone twice, let it stand, and cool down, and a light yellow solid is precipitated in the lower layer. The light yellow crude product was recrystallized from acetonitrile to obtain white crystals, which were dried in vacuo to obtain compound 6 (32.2 g, yield 89%). ¹ H-NMR (D ₂ O, 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 ); ¹³ C-NMR (D ₂ O, δ): 146.36 (NCN), 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- _CH3 ).

Example 7

Synthesis of 1,2-Dimethyl-3-dodecanol Hexafluorophosphate Ionic Liquid (7)

KPF ₆ (13.2g, 72mmol) was dissolved in 80ml of water, cooled with an ice-water bath, and then a 150ml aqueous solution of compound 6 (13.2g, 60mmol) was slowly added dropwise. After the dropwise addition, the reaction was gradually raised to room temperature for 48 hours, and the reaction was stopped. The solvent water was removed to obtain a white solid. Dissolved with 50ml CH ₂ Cl ₂ , filtered, the filtrate was washed with water (30ml×4), the organic phase was dried with anhydrous sodium sulfate, a white solid was obtained after removing the solvent, and dried in vacuo to obtain compound 7 (21.2g, yield 83% ). ¹ H-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 ); ¹³ C-NMR (DMSO, δ): 146.36 (NCN), 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 ).

Example 8

Synthesis of 1,2-Dimethyl-3-dodecyl p-toluenesulfonate Imidazolium Hexafluorophosphate Ionic Liquid (8)

Under nitrogen protection, 7 (8.53g, 20mmol) was added to a 250ml Schlenk reaction flask, dissolved in 35ml of acetonitrile, then triethylamine (3.4ml, 24mmol) was added, cooled in an ice-water bath. p-Toluenesulfonyl chloride (4.58g, 24mmol) was dissolved in 25mL of acetonitrile and added dropwise under ice-bath conditions. After the dropwise addition, the reaction was maintained at 0-5°C for 1 hour, then raised to room temperature for 24 hours, and the reaction was stopped. Filter and remove the solvent to obtain solid and dark viscous liquid, which are dissolved in 100ml CH ₂ Cl ₂ and washed with water several times, and the organic phase is dried with anhydrous Na ₂ SO ₄ . The CH ₂ Cl ₂ was removed to obtain a brownish yellow solid, which was recrystallized from acetone:ether = 2:1 to obtain a light yellow solid, which was dried in vacuo to obtain 6.40 g of the product, with a yield of 55.5%. ¹ H-NMR (DMSO, δ): 7.35 (N-CH=HC-N), 7.17 (2×CH _aryl -CS), 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, _Caryl -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 ); ¹³ C-NMR (DMSO, δ): 146.65 (C _aryl -CH ₃ ), 146.36 (NCN), 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 ).

Example 9

Synthesis of 1,2-Dimethyl-3-dodecyloxypyridinium Hexafluorophosphate Imidazolium Ionic Liquid (9)

Under nitrogen protection, 4-hydroxypyridine (0.58g, 6.05mmol) and potassium carbonate (1.25g, 9.08mmol) were added into a 100ml Schlenk reaction flask, dissolved in 20ml DMF, and heated to 80°C for 5 hours. Then a DMF (10ml) solution of 8 (2.91g, 5.00mmol) was added dropwise, stirred at 80°C for 4d, the reaction was stopped, and the system was brown. Cool and filter, remove the solvent, add 30ml of acetone and stir, filter to remove insoluble matter, remove the acetone, and recrystallize the remaining brown solid with acetone:ethyl acetate=1:1 to obtain light yellow crystals, which are dried in vacuo to obtain 1.07g of the product, the yield 43%. ¹ H-NMR (DMSO, δ): 8.25 (2H, 2×CH _Py -N), 7.35 (2H, N-CH=HC-N), 6.85 (2H, 2×CH _Py- CO), 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, _CH2 - _CH2- OH), 1.43(2H, _CH2- ( _CH2 ) ₂ -OH), 1.29(12H, N-( _CH2 ) ₂ - _CH2 ); ^13C -NMR( DMSO, δ): 156.2 (C _Py -O), 150.7 (2×CH _Py -N), 146.36 (NCN), 123.76, 122.39 (HC=CH), 100.71 (2×CH _Py -CO), 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 ).

Example 10

Synthesis of Ruthenium Catalysts Supported by Ionic Liquids Containing Pyridine Ligands(10)

Under the protection of high-purity nitrogen, add ligand 9 (200mg, 0.40mmol) to the 10ml Schlenk tube, add the second-generation Grubbs catalyst (44.2mg, 0.050mmol) to the other branch tube, and vacuumize and fill the two tubes with nitrogen respectively. three times. Dissolve the ligand 9 with 1.2ml of dry deoxygenated acetone, dissolve the catalyst with 1ml of dry CH ₂ Cl ₂ , freeze the two reaction tubes with liquid nitrogen-vacuumize-fill with nitrogen-thaw, add the catalyst solution dropwise under nitrogen atmosphere into the ligand solution. Stirring at room temperature, the system gradually changed from reddish brown to dark green, reacted for 4 hours, and stopped the reaction. Under nitrogen protection, the solvent was removed under reduced pressure to obtain a green solid. Add 1ml CH ₂ Cl ₂ , the solution is yellow-green, and the insoluble solid is green, let stand, suck out the supernatant, and discard it. The remaining solid was washed once with a little CH ₂ Cl ₂ and hexane, and dried under reduced pressure to obtain a green solid (the solid is a mixture of ligand 9 and catalyst). ¹ H-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 ); ¹³ C-NMR (DMSO, δ): 212.64 (N-CH-Ru), 165.7 (C _Py -O), 146.36 (NCN), 150.11 (2×CH _Py -N), 123.76, 122.39 (HC =CH), 100.74 (2×CH _Py -CO), 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 ). ³¹ P-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:

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

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

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

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

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

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

Described organic solvent is the mixed solvent (1.2: 1) of carrene or acetone and carrene.