CN113024611B - N-heterocyclic carbene cyclic palladium compound and preparation method and application thereof - Google Patents

N-heterocyclic carbene cyclic palladium compound and preparation method and application thereof Download PDF

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CN113024611B
CN113024611B CN202110280867.7A CN202110280867A CN113024611B CN 113024611 B CN113024611 B CN 113024611B CN 202110280867 A CN202110280867 A CN 202110280867A CN 113024611 B CN113024611 B CN 113024611B
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邓钦月
左彬
吴小强
屈二东
李万方
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University of Shanghai for Science and Technology
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Abstract

The invention discloses a nitrogen heterocyclic carbene cyclic palladium compound and a preparation method and application thereof, belonging to the technical field of organic catalysis. The N-heterocyclic carbene cyclic palladium compound is prepared by the following steps: heating, stirring and mixing N- (4-butoxybenzyl) -N-ethyl ethylamine, palladium chloride and an organic solvent under the inert gas atmosphere, adding potassium carbonate, stirring and mixing, and finally adding 1- (2, 6-diisopropylphenyl) -3-butyl-imidazole bromide for reflux reaction; after the reaction is finished, quenching the reaction product by using an acidic solution, extracting to obtain a crude product, and separating and purifying by column chromatography to obtain the N-heterocyclic carbene cyclic palladium compound. The N-heterocyclic carbene cyclic palladium compound has high catalytic activity, can catalyze the cross coupling reaction between aryl chloride and aryl phenylboronic acid, aryl chloride and secondary amine with high difficulty by using a catalytic amount of 1mol%, and can be used as a high-efficiency catalyst for the coupling reaction.

Description

N-heterocyclic carbene cyclic palladium compound and preparation method and application thereof
Technical Field
The invention relates to a nitrogen heterocyclic carbene cyclic palladium compound and a preparation method and application thereof, belonging to the technical field of organic catalysis.
Background
Since Aduengo first isolated free N-heterocyclic carbenes in 1991, various N-heterocyclic carbene metal complexes have been reported. Due to the excellent characteristics of easy preparation, strong sigma-electron donating capability, capability of forming stable carbon-metal bonds with transition metals and the like, N-heterocyclic carbene (NHC) ligands attract wide attention in transition metal catalysis. The N-heterocyclic carbene forms metal complexes with various structures through coordination with metal ions. Compared with phosphine ligand, the N-heterocyclic carbene ligand has the advantages of higher thermal stability, water resistance, air stability, lower toxicity and the like.
In the field of organic catalysis, the N-heterocyclic carbene metal complex can catalyze a wide variety of reactions, and the catalytic effect is obviously superior to that of metal complexes formed by other phosphine ligands with similar structures. Such as high-efficiency catalysis of carbon-carbon bond Suzuki-Miyaura coupling reaction, carbon-nitrogen bond Buchwald-Hartwig coupling reaction and the like. The N-heterocyclic carbene-palladium compound is widely applied to the fields of biomedicine, functional materials and the like.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: how to obtain a nitrogen heterocyclic carbene catalyst with stable structure, hydrophilicity and high catalytic activity.
In order to solve the problems, the invention provides a nitrogen heterocyclic carbene cyclic palladium compound, which has a chemical structural formula as follows:
Figure 205449DEST_PATH_IMAGE001
the invention also provides a preparation method of the N-heterocyclic carbene cyclic palladium compound, which comprises the following steps:
step 1: mixing N- (4-butoxybenzyl) -N-ethyl ethylamine, palladium chloride and an organic solvent in an inert gas atmosphere, and heating and stirring to obtain a mixed solution;
step 2: adding carbonate into the mixed solution, stirring and mixing, and then adding 1- (2, 6-diisopropylphenyl) -3-butyl-imidazole bromide for reflux reaction;
and 3, step 3: and after the reaction is finished, quenching the reaction product by using an acidic solution, extracting to obtain a crude product, and separating and purifying to obtain the N-heterocyclic carbene cyclic palladium compound.
Preferably, the organic solvent in step 1 is one or a mixture of methanol, 1, 4-dioxane, acetone, dichloromethane and acetonitrile.
Preferably, the molar ratio of the N- (4-butoxybenzyl) -N-ethyl ethylamine to the palladium chloride in the step 1 is 1 to 1.2, and the concentration of the palladium chloride in the mixed solution is 0.02 to 0.1mol/L.
Preferably, the heating and stirring in the step 1 are carried out at the temperature of 70 to 90 ℃ for 0.5 to 1h.
Preferably, the molar ratio of the carbonate salt in step 2, 1- (2, 6-diisopropylphenyl) -3-butyl-imidazolium bromide and N- (4-butoxybenzyl) -N-ethylethylamine is 0.4.
Preferably, the stirring and mixing time in the step 2 is 0.5 to 1h, and the reflux reaction time is 20 to 30h.
Preferably, the acidic solution in the step 3 is a5 to 20wt% hydrochloric acid solution; the solvent adopted for extraction is dichloromethane and/or chloroform; the method adopted for separation and purification is silica gel column chromatography.
The invention also provides application of the N-heterocyclic carbene cyclic palladium compound.
Preferably, said use comprises use in Suzuki-Miyaura coupling reactions and in Buchwald-Hartwig coupling reactions.
Compared with the prior art, the invention has the beneficial effects that:
1. the N-heterocyclic carbene cyclic palladium compound has stable structure and high catalytic activity, and can be used as a high-efficiency catalyst to be applied to Suzuki-Miyaura coupling reaction and Buchwald-Hartwig coupling reaction;
2. the N-heterocyclic carbene cyclic palladium compound is synthesized into an anti-Parkinson medicament Pirbestail with a yield of more than 90 percent under the catalytic amount of 1mol percent.
3. The preparation method is simple and has mild reaction conditions.
Drawings
FIG. 1 is a single crystal structure diagram of the N-heterocyclic carbene cyclic palladium compound of the invention.
Detailed Description
In order to make the present invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.
Example 1
A preparation method of an N-heterocyclic carbene cyclic palladium compound is shown as Scheme 1, and comprises the following steps:
step 1: preparation of 2, 6-diisopropylimidazole (a 1) 2, 6-diisopropylaniline (50 mmol) and glyoxal (50 mmol) were dissolved in MeOH (20 mL) and stirred at 25 ℃ for 12 h. Ammonium dichloride (100 mmol) and formaldehyde (100 mmol) (37% aqueous formaldehyde) were then added and diluted with MeOH (200 mL), heated at reflux for 1H at 65 deg.C, and 86% H was added dropwise 3 PO 4 (7 ml) and the reaction was refluxed for 8 hours. After the reaction is finished, removing part of solvent by rotary evaporation until the reaction mixture is concentrated to 30-40 mL, transferring the reaction mixture into a beaker, adding ice cubes, adjusting the pH to 9 by using 8M NaOH solution, extracting by EA, collecting an organic phase, washing the organic phase by using water and saturated saline water respectively, and then washing the organic phase by using anhydrous Na 2 SO 4 And (5) drying. And after spin-drying, separating the obtained crude product by column chromatography to obtain a pure 2, 6-diisopropyl imidazole product. Nuclear magnetic analysis: 1 H NMR (400 MHz，CDCl3，298 K): δ= 9.88 (s，1H)，7.83 (d，J = 8.0 Hz，2H)，6.99 (d，J = 8.0 Hz，2H)，4.04 (t，J = 6.5 Hz，2H)，3.41 (t，J = 6.8 Hz，2H)，1.90-1.76 (m，4H)，1.44 (dt，J = 15.3，7.5 Hz，4H)，1.29 (s，12H)； 13 C NMR (101 MHz，CDCl3，298 K): δ= 190.80，164.29，131.99，129.79，114.77，68.44，34.02，32.84，29.51，29.42，29.32，29.06，28.76，28.17，25.96。
and 2, step: preparation of the imidazolium salt (a 2) 2, 6-diisopropylimidazole (4 mmol) and 1-bromobutane (8.8 mmol) were dissolved in 40mL of 1, 4-dioxane and stirred at 95 ℃ under reflux for 3 h. 2, 6-diisopropylimidazole (4 mmol) was then added in two portions and the reaction was continued for 24 hours. And the crude product of the reaction is separated by column chromatography to obtain the pure product of the imidazole salt. Nuclear magnetic analysis: 1 H NMR (400 MHz，CDCl3，298 K): δ= 10.43 (s，1H)，8.02 (s，1H)，7.54 (t，J = 7.5 Hz，1H)，7.30 (d，J = 8.6 Hz，3H)，4.80 (t，J = 6.8 Hz，2H)，2.34- 2.20 (m，2H)，2.06-1.94 (m，3H)，1.42 (dd，J = 14.7，7.3 Hz，2H)，1.23 (d，J = 6.6 Hz，6H)，1.16 (d，J = 7.0 Hz，7H)，0.99 (t，J = 7.1 Hz，3H)； 13 C NMR (101 MHz，CDCl3，298 K): δ= 145.28，138.22，131.74，130.14，124.53，124.17，123.18，50.02，32.40，28.63，24.33，24.00，19.16，13.44。
and 3, step 3: preparation of 4-Butoxybenzaldehyde (a 3) 1-bromobutane (11 mmol), p-hydroxybenzaldehyde (5 mmol) and anhydrous potassium carbonate (20 mmol) were added to a solution of acetone (75 mL) and then stirred at reflux at 65 ℃ for 3 h. Hydroxybenzaldehyde (5 mmol) was then added in two portions and the reaction was continued for 15 hours. Finally, the pure 4-butoxybenzaldehyde is obtained by column chromatography separation. Nuclear magnetic analysis: 1 H NMR (400 MHz，CDCl3，298 K): δ= 9.88 (s，1H)，7.83 (d，J = 8.1 Hz，2H)，6.99 (d，J = 8.0 Hz，2H)，4.05 (t，J = 6.5 Hz，2H)，1.83-1.77 (m，2H)，1.55- 1.49 (m，2H)，0.98 (d，J = 7.2 Hz，3H)； 13 C NMR (101 MHz，CDCl3，298 K): δ= 190.78，164.25，131.94，129.71，114.71，68.07，31.04，19.12，13.74。
and 4, step 4: preparation of N- (4-butoxybenzyl) -N-ethylethylamine (a 4) 4-butoxybenzaldehyde (5 mmol) and diethylamine (15 mmol) (about 1.55 mL) were dissolved in DCM (50 mL) and stirred at room temperature for 1h. Sodium triacetoxyborohydride (20 mmol) was then added and stirred at room temperature for 18 hours. After the reaction is finished, 1M NaHCO is used 3 The aqueous solution (25 mL) was quenched and then transferred to a separatory funnel, extracted with DCM, and the lower organic phase was collected and washed with distilled water and saturated brine, dried over anhydrous sodium sulfate, and spin-dried to give the crude product. The crude product is separated by column chromatography to obtain a pure product. Nuclear magnetic analysis: 1 H NMR (400 MHz，CDCl3，298 K): δ= 7.42 (d，J = 7.9 Hz，2H)，6.90 (d，J = 7.7 Hz，2H)，3.97 (d，J = 6.3 Hz，2H)，3.94 (s，2H)，2.89 (d，J = 6.7 Hz，4H)，1.81-1.72 (m，2H)，1.49 (dd，J = 14.3，7.4 Hz，2H)，1.31 (t，J = 6.6 Hz，6H)，0.98 (t，J = 7.2 Hz，3H)； 13 C NMR (101 MHz，CDCl3，298 K): δ= 159.27，131.40，114.64，67.70，55.52，45.61，31.24，19.19，13.78，9.82。
and 5: preparation of N-heterocyclic carbene cyclic palladium compound (a 5), N- (4-butoxybenzyl) -N-ethyl ethylamine (1.05 mmol) and PdCl under nitrogen protection 2 (1 mmol) was added to a 50 mL Schlenk tube, andinto CH 3 CN (20 mL) was stirred in an oil bath at 80 ℃ for half an hour, then powdered K was added 2 CO 3 (0.5 mmol) and stirred for half an hour. Then imidazole salt (1.05 mmol) is added, reflux reaction is continued for 24 hours, 10wt% of dilute hydrochloric acid is added for quenching after the reaction is finished, chloroform extraction is carried out, the organic phase is washed by water and saturated salt water respectively, drying is carried out by anhydrous sodium sulfate, solvent is removed by rotary evaporation to obtain a crude product, and a pure product is obtained by column chromatography separation, wherein the structure diagram of a single crystal of the pure product is shown in figure 1. Nuclear magnetic analysis: 1 H NMR (400 MHz，CDCl3，298 K): δ= 7.37 (t，J = 7.6 Hz，1H)，7.29 (s，1H)，7.20 (s，1H)，7.07 (d，J = 7.6 Hz，1H)， 6.99 (s，1H)，6.74 (d，J = 8.3 Hz，1H)，6.42 (d，J = 8.0 Hz，1H)，5.87 (s，1H)，4.78 (t，J = 14.7 Hz，1H)，4.54 (t，J = 14.6Hz，1H)，4.04 (d，J = 14.4 Hz，1H)，3.77 (dd，J = 15.7，8.2 Hz，2H)，3.35-2.94 (m，4H)，2.76 (dd，J = 12.4，6.7 Hz，1H)，2.60-2.48 (m，1H)，2.38-2.20 (m，2H)，2.03 (s，1H)，1.74-1.61 (m，2H)，1.51 (d，J = 7.0 Hz，2H)，1.44 (d，J = 7.3 Hz，2H)，1.39 (d，J = 6.6 Hz，3H)，1.20 (t，J = 7.1 Hz，3H)，1.02 (dd，J = 16.7，7.0 Hz，9H)，0.95 (t，J = 7.3 Hz，3H)，0.88 (d，J = 6.7 Hz，3H)，0.30 (d，J = 6.5 Hz，3H)； 13 C NMR (101 MHz，CDCl3，298 K): δ = 155.68，150.91，147.73，146.14，143.11，129.60，124.81，123.70，123.26，121.76，121.11，119.51，108.99，67.28，63.15，55.77，53.75，51.80，32.03，31.47，28.46，26.79，26.10，23.05，20.62，20.33，19.32，13.84，12.96，11.69。
Figure 69500DEST_PATH_IMAGE002
Scheme 1
application example 1
Preparation of 4-methoxybiphenyl:
under a nitrogen atmosphere, 4-methoxyphenylboronic acid (0.75 mmol) was used to take out the azacyclo-carbene cyclopalladated compound prepared in example 1 (1 mol%), K 2 CO 3 (1.5 equiv.) and EtOH/H 2 O (2.0 mL) was added to the Schlenk reaction tube followed by chlorobenzene (0.5 mmol). The mixture was stirred at 60 ℃ for 12h, then extracted with EtOAc and over anhydrous Na 2 SO 4 Drying, filtering, and removing the solvent by rotary evaporation to obtain a crude product, and separating by flash column chromatography to obtain pure 4-methoxybiphenyl with the yield of 93%. Nuclear magnetic analysis: 1 H NMR (400 MHz，CDCl 3 ，298 K): δ = 7.59-7.49 (m，4H)，7.42 (t，J = 7.7 Hz，2H)， 7.29 (d， J = 7.3 Hz，1H)， 6.98 (d，J = 8.8 Hz，2H)，3.86 (s，3H)； 13 C NMR (101 MHz，CDCl 3 ， 298 K): δ = 159.15， 140.83， 133.80， 128.70， 128.14， 126.73， 126.64， 114.20， 55.34。
the above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way and substantially, it should be noted that those skilled in the art may make several modifications and additions without departing from the scope of the present invention, which should also be construed as a protection scope of the present invention.

Claims (8)

1. A N-heterocyclic carbene cyclic palladium compound is characterized in that the chemical structural formula is as follows:
Figure 273918DEST_PATH_IMAGE001
。
2. the preparation method of the N-heterocyclic carbene cyclic palladium compound as described in claim 1, characterized by comprising the steps of:
step 1: mixing N- (4-butoxybenzyl) -N-ethyl ethylamine, palladium chloride and an organic solvent in an inert gas atmosphere, and heating and stirring to obtain a mixed solution;
step 2: adding carbonate into the mixed solution, stirring and mixing, and then adding 1- (2, 6-diisopropylphenyl) -3-butyl-imidazole bromide for reflux reaction;
and 3, step 3: and after the reaction is finished, quenching the reaction product by using an acidic solution, extracting to obtain a crude product, and separating and purifying to obtain the N-heterocyclic carbene cyclic palladium compound.
3. The method for preparing the N-heterocyclic carbene cyclic palladium compound as claimed in claim 2, wherein the organic solvent in the step 1 is one or a mixture of several of methanol, 1, 4-dioxane, acetone, dichloromethane and acetonitrile.
4. The method for preparing an N-heterocyclic carbene cyclopalladated compound as claimed in claim 2, wherein the molar ratio of N- (4-butoxybenzyl) -N-ethyl ethylamine to palladium chloride in the step 1 is 1 to 1.2, and the concentration of the palladium chloride in the mixed solution is 0.02 to 0.1mol/L.
5. The preparation method of the N-heterocyclic carbene cyclic palladium compound as claimed in claim 2, wherein the heating and stirring in the step 1 are carried out at 70 to 90 ℃ for 0.5 to 1h.
6. The method for preparing an azacyclo-carbene cyclopalladated compound according to claim 2, wherein the molar ratio of the carbonate in the step 2, 1- (2, 6-diisopropylphenyl) -3-butyl-imidazole bromide and the N- (4-butoxybenzyl) -N-ethyl-amine in the step 1 is 0.4.
7. The preparation method of the N-heterocyclic carbene cyclic palladium compound as claimed in claim 2, wherein the stirring and mixing time in the step 2 is 0.5 to 1h, and the reflux reaction time is 20 to 30h.
8. The method for preparing an N-heterocyclic carbene cyclic palladium compound as set forth in claim 2, wherein the acidic solution in the step 3 is a5 to 20wt% hydrochloric acid solution; the solvent adopted for extraction is dichloromethane and/or chloroform; the separation and purification method is a silica gel column chromatography.
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