CN104151364A - O-pyrazolyl phenyl functionalized nitrogen heterocyclic carbene palladium complex and preparation method and application thereof - Google Patents
O-pyrazolyl phenyl functionalized nitrogen heterocyclic carbene palladium complex and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to an o-pyrazolyl phenyl functionalized nitrogen heterocyclic carbene palladium complex and a preparation method and application thereof. The preparation method of the nitrogen heterocyclic carbene palladium complex is as follows: at room temperature in dark conditions, an o-pyrazolyl phenyl substituted imidazolium salt is reacted with silver oxide to prepare a corresponding nitrogen heterocyclic carbene silver complex, then metallization conversion reaction of the corresponding nitrogen heterocyclic carbene silver complex and bis(acetonitrile)dichloropalladium(II) is performed; or the o-pyrazolyl phenyl substituted imidazolium salt is directly reacted with palladium acetate for preparation of the nitrogen heterocyclic carbene palladium complex. The nitrogen heterocyclic carbene palladium complex has efficient capability of catalyzing of formation of carbon-carbon bonds, and can be mainly used in organic catalysis technology field.
Description
Technical field:
The invention belongs to organic synthesis and Organometallic Chemistry technical field, relate to the synthetic and application of N-heterocyclic carbine palladium complex, preparation method and the application of the N-heterocyclic carbine palladium complex that the imidazole salts that is in particular adjacent pyrazolyl phenyl functionalization is precursor.
Background technology:
Because it is successfully applied to coordination chemistry and homogeneous catalysis, N-heterocyclic carbine and transition metal complex thereof have been subject in recent years people and have paid close attention to widely, have become one of focus of people's research.N-heterocyclic carbine metal title complex often has higher activity and stability than corresponding containing phosphine ligand compound, makes it in transition metal-catalyzed linked reaction, obtain larger development.Recently, the N-heterocyclic carbine of heteroatoms functionalization has also caused that people more and more note.Due to heteroatomic introducing, the N-heterocyclic carbine metal title complex of these functionalization shows relatively high stability and catalytic activity.Meanwhile, also facilitate the substituting group by changing on heterocycle skeleton to regulate solid and the electronic effect in N-heterocyclic carbine metal title complex, and this is even more important for activity and selectivity of improving catalyzer.Pyrazoles is the organic ligand that a class has extensive coordination ability, and the substituting group that its coordination ability also easily encircles by change is regulated and controled, and this is conducive to greatly people and finds new efficient catalyzer and explore some new chemical reactions.
Summary of the invention:
The object of the present invention is to provide the N-heterocyclic carbine palladium complex and preparation method thereof and application of adjacent pyrazolyl phenyl functionalization.The present invention also relates to prepare the method for this type of N-heterocyclic carbine palladium complex precursor.The present invention further relates to this type of application of N-heterocyclic carbine palladium complex in catalytic field.
The synthetic method of the N-heterocyclic carbine palladium complex of the adjacent pyrazolyl phenyl functionalization in the present invention, synthesis technique comprises the following steps:
(1) imidazoles of adjacent pyrazolyl phenyl functionalization and halohydrocarbon are reacted for 1: 1 in molar ratio, make the imidazole salts of corresponding adjacent pyrazolyl phenyl functionalization;
(2) imidazole salts of adjacent pyrazolyl phenyl functionalization step (1) being made is mixed with silver suboxide, adds methylene dichloride, at room temperature lucifuge reaction 24 hours.Then add di acetonitrile palladium chloride, under room temperature, continue reaction 24 hours.Filter, concentrated, column chromatography purification.Make the N-heterocyclic carbine palladium complex of adjacent pyrazolyl phenyl functionalization; Wherein the mol ratio of imidazole salts, silver suboxide and the di acetonitrile palladium chloride of adjacent pyrazolyl phenyl functionalization is: 1: 1: 1;
(3) imidazole salts of adjacent pyrazolyl phenyl functionalization step (1) being made be take the ratio that mol ratio is 1: 1 and is mixed with palladium, add methylene dichloride, and under room temperature, stirring reaction is 24 hours.Filter, concentrate, make the N-heterocyclic carbine palladium complex of corresponding adjacent pyrazolyl phenyl functionalization.
The imidazoles of above-mentioned adjacent pyrazolyl phenyl functionalization is 1-[2-(pyrazol-1-yl) phenyl] imidazoles, 1-[2-(3,5-dimethyl pyrazole-1-yl) phenyl] imidazoles, 1-[2-(3,5-di-isopropyl pyrazol-1-yl) phenyl] imidazoles: halohydrocarbon is: methyl iodide, monobromethane, 2-N-PROPYLE BROMIDE, 2-iodopropane, Benzyl Chloride.
The present invention adopts the means such as nucleus magnetic resonance to characterize N-heterocyclic carbine palladium complex and the precursor thereof of the adjacent pyrazolyl phenyl functionalization of synthesized.The resulting N-heterocyclic carbine palladium complex of the present invention has efficient catalytic activity, is expected to obtain further Application and Development in catalytic field.
Accompanying drawing explanation:
The crystalline structure figure of the N-heterocyclic carbine palladium complex (1) of Fig. 1, adjacent pyrazolyl phenyl functionalization
The crystalline structure figure of the N-heterocyclic carbine palladium complex (2) of Fig. 2, adjacent pyrazolyl phenyl functionalization
Embodiment:
Embodiment 1
Chloro N-1-[2-(pyrazol-1-yl) phenyl]-N '-benzyl imidazole salt synthetic
In 10mL round-bottomed flask, add successively 2mL acetonitrile, 1-[2-(pyrazol-1-yl) phenyl] imidazoles 0.21g (1.0mmol), Benzyl Chloride 0.12mL (1.0mmol).Reaction mixture stirring and refluxing was chilled to room temperature after 24 hours.Decompression is lower, and except desolventizing, resistates washs with anhydrous diethyl ether, and vacuum-drying obtains oily product 0.32g, productive rate 94%.
1H?NMR(400MHz，CDCl
3)：δ5.74(s，2H)，6.37(s，1H)，6.98(s，1H)，7.36-7.40(m，4H)，7.54-7.59(m，5H)，7.63-7.68(m，1H)，7.74(s，1H)，7.82(d，1H)，10.61(s，1H)。
Synthesizing of the N-heterocyclic carbine palladium complex (1) of adjacent pyrazolyl phenyl functionalization
In 50mL round-bottomed flask, add successively 20mL methylene dichloride, chloro N-1-[2-(pyrazol-1-yl) phenyl]-N '-benzyl imidazole salt 0.50g (1.5mmol), silver suboxide 0.35g (1.5mmol).Under reaction mixture room temperature, lucifuge stirs 24 hours.Then di acetonitrile palladium chloride 0.39g (1.5mmol) is added in above-mentioned reaction system, room temperature continues stirring reaction 24 hours.Filter, under filtrate decompression, be concentrated into dry.Methylene dichloride/ethanol for resistates (volume ratio 20: 1) is eluent, crosses silicagel column, obtains 0.43g faint yellow solid product, productive rate 60%.
1H?NMR(400MHz，DMSO-d
6)：δ5.39(d，1H)，6.05(d，1H)，6.69(s，1H)，7.36-7.44(m，3H)，7.55(d，2H)，7.67(s，1H)，7.75-7.87(m，4H)，7.92(d，2H)，8.39(s，1H)。
Embodiment 2
Iodo N-1-[2-(3，5-dimethylpyrazole-1-yl) phenyl]-N '-isopropylimdazole salt synthetic
In 50mL round-bottomed flask, add successively 5mL acetonitrile, 1-[2-(3，5-dimethylpyrazole-1-yl) phenyl] imidazoles 0.47g (2.0mmol), Iso-Propyl iodide 0.24mL (2.0mmol).Reaction mixture stirring and refluxing was chilled to room temperature after 24 hours, added 20mL ethyl acetate, separated out solid.Filter, solid washs with anhydrous diethyl ether, and vacuum-drying obtains 0.80g faint yellow solid product, productive rate 97%.
1H?NMR(400MHz，CDCl
3)：δ1.61(d，6H)，2.08(s，3H)，2.18(s，3H)，5.26(septet，1H)，5.97(s，1H)，7.07(s，1H)，7.48-7.63(m，4H)，8.09-8.13(m，1H)，10.29(s，1H)。
Synthesizing of the N-heterocyclic carbine palladium complex (2) of adjacent pyrazolyl phenyl functionalization
In 50mL round-bottomed flask, add successively 20mL methylene dichloride, iodo N-1-[2-(3，5-dimethylpyrazole-1-yl) phenyl]-N '-isopropylimdazole salt 0.41g (1.0mmol), palladium 0.22g (1.0mmol).Reaction mixture stirring at room reaction 24 hours, is then concentrated into dry under decompression.Resistates washs with anhydrous diethyl ether, and vacuum-drying obtains 0.49g yellow solid product, productive rate 86%.
1H?NMR(400MHz，CDCl
3)：δ1.41(d，3H)，1.51(d，3H)，1.82(s，3H)，2.04(s，3H)，5.74(septet，1H)，6.03(s，1H)，7.04(s，1H)，7.17(s，1H)，7.61-7.76(m，4H)。
Embodiment 3
The general procedure of catalysis Suzuki linked reaction: in 10mL round-bottomed flask, add successively phenylo boric acid 0.15g (1.2mmol), cesium carbonate 0.66g (2.0mmol), halogenated aryl hydrocarbon (1.0mmol), 2mL isopropanol/water mixed solvent (volume ratio 1: 1), a certain amount of N-heterocyclic carbine palladium complex (1) or (2) (n mol%).Reaction mixture is in the reaction times of 80 ℃ of stirring reaction appointments.Be chilled to room temperature, add 5mL water, then use ether (3 * 10mL) extraction.Merge organic layer, use anhydrous sodium sulfate drying.Filter, under filtrate decompression, except desolventizing, sherwood oil for resistates (60-90 ℃), as eluent, is crossed silicagel column, obtains corresponding biphenyl derivatives product.
The N-heterocyclic carbine palladium complex 1 that the embodiment 1 and 2 of usining obtains and 2 the results are shown in Table 1 as catalyst Suzuki linked reaction.
The Suzuki linked reaction of table 1 N-heterocyclic carbine palladium complex 1 and 2 catalysis is active
Embodiment 4
The general procedure of catalytic Heck coupling reaction: in 10mL round-bottomed flask, add successively a certain amount of N-heterocyclic carbine palladium complex (1) or (2) (n mol%), salt of wormwood (2.0mmol), halogenated aryl hydrocarbon (1.0mmol), vinylbenzene 0.14mL (1.2mmol), 2mL DMF/water mixed solvent (volume ratio 3: l).Reaction mixture was 120 ℃ of stirring reactions 24 hours.Be chilled to room temperature, decompression is lower to desolventizing, and ethyl acetate/petroleum ether resistates for (60-90 ℃) (volume ratio 1: 3), as eluent, is crossed silicagel column, obtain accordingly trans-1,2-diarylethene product.
The N-heterocyclic carbine palladium complex 1 that the embodiment 1 and 2 of usining obtains and 2 the results are shown in Table 2 as catalyst Heck linked reaction.
The Heck linked reaction of table 2 N-heterocyclic carbine palladium complex 1 and 2 catalysis is active
Above embodiment is only for illustrating content of the present invention, and unrestricted the present invention, knowledgeable people in same area can propose easily other embodiment within technical director's thought of the present invention, but this embodiment comprises within the scope of the present invention.
Claims (4)
1. the N-heterocyclic carbine palladium complex of adjacent pyrazolyl phenyl functionalization, is characterized in that its structural formula is as follows:
Wherein: R is for being selected from hydrogen, methyl and sec.-propyl; R ' is for being selected from methyl, ethyl, sec.-propyl and benzyl; X is for being selected from chlorine, bromine and iodine; X ' is for being selected from chlorine, bromine, iodine and acetate.
2. the method for N-heterocyclic carbine palladium complex of adjacent pyrazolyl phenyl functionalization described in preparation claim 1, is characterized in that synthesis technique comprises the following steps:
(1) imidazoles of adjacent pyrazolyl phenyl functionalization and halohydrocarbon are reacted for 1: 1 in molar ratio, make the imidazole salts of corresponding adjacent pyrazolyl phenyl functionalization;
(2) imidazole salts of adjacent pyrazolyl phenyl functionalization step (1) being made is mixed with silver suboxide, adds methylene dichloride, at room temperature lucifuge reaction 24 hours.Then add di acetonitrile palladium chloride, under room temperature, continue reaction 24 hours.Filter, concentrated, column chromatography purification.Make the N-heterocyclic carbine palladium complex of adjacent pyrazolyl phenyl functionalization; Wherein the mol ratio of imidazole salts, silver suboxide and the di acetonitrile palladium chloride of adjacent pyrazolyl phenyl functionalization is: 1: 1: 1;
(3) imidazole salts of adjacent pyrazolyl phenyl functionalization step (1) being made be take the ratio that mol ratio is 1: 1 and is mixed with palladium, add methylene dichloride, and under room temperature, stirring reaction is 24 hours.Filter, concentrate, make the N-heterocyclic carbine palladium complex of corresponding adjacent pyrazolyl phenyl functionalization.
3. method according to claim 2, the imidazoles of wherein said adjacent pyrazolyl phenyl functionalization is 1-[2-(pyrazol-1-yl) phenyl] imidazoles, 1-[2-(3,5-dimethyl pyrazole-1-yl) phenyl] imidazoles, 1-[2-(3,5-di-isopropyl pyrazol-1-yl) phenyl] imidazoles: halohydrocarbon is: methyl iodide, monobromethane, 2-N-PROPYLE BROMIDE, 2-iodopropane, Benzyl Chloride.
4. the application of the N-heterocyclic carbine palladium complex of adjacent pyrazolyl phenyl functionalization in Kaolinite Preparation of Catalyst field described in claim 1.
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Cited By (7)
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|---|---|---|---|---|
| CN108380245A (en) * | 2018-02-06 | 2018-08-10 | 中山大学 | A kind of novel bidentate phosphorus-azepine Cabbeen p-cymene type catalyzed by ruthenium complexes agent and preparation method thereof and synthesis application |
| CN108586345A (en) * | 2018-02-05 | 2018-09-28 | 天津师范大学 | N-heterocyclic carbine palladium complex and preparation method thereof and purposes |
| CN110898856A (en) * | 2019-10-24 | 2020-03-24 | 沈阳化工大学 | Pd (II) -NHC catalyst preparation method and application in Suzuki-Miyaura reaction |
| CN113816999A (en) * | 2021-10-27 | 2021-12-21 | 常州大学 | Caffeine-derived azacyclo-carbene-palladium complex and synthesis method and catalytic application thereof |
| CN113856764A (en) * | 2021-10-29 | 2021-12-31 | 华中科技大学 | Transition metal catalyst and preparation method and application thereof |
| CN115722266A (en) * | 2022-11-24 | 2023-03-03 | 广东药科大学 | Novel aza-carbene-amido-ruthenium catalyst and preparation method and application thereof |
| CN116332964A (en) * | 2022-10-30 | 2023-06-27 | 西北大学 | Synthesis method of bidentate pyrazolyl nitrogen heterocyclic palladium carbene compound |
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2013
- 2013-05-13 CN CN201310172938.7A patent/CN104151364A/en active Pending
Non-Patent Citations (2)
| Title |
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| RUIHU WANG ET AL.: "A Highly Efficient, Recyclable Catalyst for C-C Coupling Reactions in Ionic Liquids: Pyrazolyl-Functionalized N-Heterocyclic Carbene Complex of Palladium(II)", 《J. ORG. CHEM.》 * |
| 程才红等: "吡唑功能化的氮杂环卡宾与过渡金属的相关反应研究", 《中国化学会第28届学术年会论文集》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108586345A (en) * | 2018-02-05 | 2018-09-28 | 天津师范大学 | N-heterocyclic carbine palladium complex and preparation method thereof and purposes |
| CN108380245A (en) * | 2018-02-06 | 2018-08-10 | 中山大学 | A kind of novel bidentate phosphorus-azepine Cabbeen p-cymene type catalyzed by ruthenium complexes agent and preparation method thereof and synthesis application |
| CN108380245B (en) * | 2018-02-06 | 2020-06-09 | 中山大学 | Bidentate phosphorus-aza-carbene p-cymene type ruthenium complex catalyst, preparation method and synthesis application thereof |
| CN110898856A (en) * | 2019-10-24 | 2020-03-24 | 沈阳化工大学 | Pd (II) -NHC catalyst preparation method and application in Suzuki-Miyaura reaction |
| CN110898856B (en) * | 2019-10-24 | 2022-10-18 | 沈阳化工大学 | Preparation method of Pd (II) -NHC catalyst and application of Pd (II) -NHC catalyst in Suzuki-Miyaura reaction |
| CN113816999A (en) * | 2021-10-27 | 2021-12-21 | 常州大学 | Caffeine-derived azacyclo-carbene-palladium complex and synthesis method and catalytic application thereof |
| CN113816999B (en) * | 2021-10-27 | 2022-08-26 | 常州大学 | Caffeine-derived azacyclo-carbene-palladium complex and synthesis method and catalytic application thereof |
| CN113856764A (en) * | 2021-10-29 | 2021-12-31 | 华中科技大学 | Transition metal catalyst and preparation method and application thereof |
| CN116332964A (en) * | 2022-10-30 | 2023-06-27 | 西北大学 | Synthesis method of bidentate pyrazolyl nitrogen heterocyclic palladium carbene compound |
| CN115722266A (en) * | 2022-11-24 | 2023-03-03 | 广东药科大学 | Novel aza-carbene-amido-ruthenium catalyst and preparation method and application thereof |
| CN115722266B (en) * | 2022-11-24 | 2024-04-05 | 广东药科大学 | Azacarbene-amino-ruthenium catalyst, and preparation method and application thereof |
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Application publication date: 20141119 |