CN102627672A - N-heterocyclic carbine palladium compound containing pyridyl-2-formate or pyridyl-2,6-diformate ligand, preparation thereof and application thereof - Google Patents
N-heterocyclic carbine palladium compound containing pyridyl-2-formate or pyridyl-2,6-diformate ligand, preparation thereof and application thereof Download PDFInfo
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- 0 Cc1cc(C)c(*(C2*(*3c4cccc3)OC4=O)C=C=*2c2c(C)cc(C)cc2C)c(C)c1 Chemical compound Cc1cc(C)c(*(C2*(*3c4cccc3)OC4=O)C=C=*2c2c(C)cc(C)cc2C)c(C)c1 0.000 description 2
Abstract
The invention relates to a preparation method and an application of an N-heterocyclic carbine palladium compound containing a pyridyl-2-formate or pyridyl-2,6-diformate ligand. The N-heterocyclic carbine palladium compound containing the pyridyl-2-formate or pyridyl-2,6-diformate ligand is generated by reacting initial raw materials of a substituted imidazolium or imidazolium salt, palladium chloride and 2-picolinic acid or 2,6-dipicolinic acid, or the N-heterocyclic carbine palladium compound is generated in a high yield manner by using a corresponding N-heterocyclic carbine palladium chloride dipolymer and 2-picolinic acid or 2,6-dipicolinic acid as initial raw materials. The N-heterocyclic carbine palladium compound of the invention has a very high catalytic activity when being used in a C-N cross-coupling reaction of a halogenated arene and an organic amine as a catalyst. The chemical structural formula of the N-heterocyclic carbine palladium compound containing the pyridyl-2-formate or pyridyl-2,6-diformate ligand is shown in the specification. In the chemical structural formula, m is 0-4, and n is 0-3; and carbon numbers of R<1>, R<2>, R<3>, R<4> and R<5> are defined in the claim 1.
Description
Technical field
The present invention relates to a kind of pyridine-2-formate or pyridine-2 of containing, N-heterocyclic carbine palladium mixture and the preparation method and the application thereof of the two formate parts of 6-.This N-heterocyclic carbine palladium mixture can be used as the C-N cross-coupling reaction that catalyzer is used for halogenated aryl hydrocarbon and organic amine, has very high catalytic activity.Especially the C-N cross-coupling reaction that has than large space sterically hindered chlorinated aromatic hydrocarbons and organic amine is had high activity, this is one of catalyzer the most efficiently in the at present transition metal-catalyzed C-N cross-coupling reaction.
Background technology
Aromatic amine compounds is according to its constitutional features, is widely used in pharmacy, optics and electricity material and as the purposes such as part of transition metal ion.Although aromatic amine compounds is simple in structure, it is synthetic relatively more difficult usually.Generally need nitrated, reduction, and the existence of some functional group also can hinder substitution reaction; Reductive amination method is applicable to the substituted arylamine of some alkyl of preparation, but this reaction needed is pre-existing in a fragrant C-N key; And the direct nucleophilic substitution reaction of halogenated aryl hydrocarbon needs intensive polar solvent, high temperature usually or adopts the activatory halogenated aryl hydrocarbon.Though adopt the catalytic Ullmann of traditional copper reaction also can carry out substitution reaction, yet reaction need could take place usually under the condition that heats up, and the existence of responsive functional group also is unfavorable for the carrying out that react.In addition, the diaryl reaction takes place through regular meeting in the uncle's arylamine that adopts this method to obtain, and generates by product.Therefore; The catalytic C-N cross-coupling reaction of research and development novel transition metal synthetic aroma aminated compounds is focus (the Ackermann L. Ed.Modern Arylation Methods in the Synthetic Organic Chemistry research field all the time; Wiley-VCH:Weinheim, Germany, 2009).Compare with traditional copper catalyzed reaction, transition metal palladium, nickel etc. have advantages such as more efficient, that the substrate scope of application is wider as catalyst applications in the C-N binding reaction.As far back as nineteen eighty-three, Migita etc. have reported that amino tin of tributyl and aryl bromide reaction can prepare aromatic amine compound under palladium catalysis, and this reaction is applicable to dialkylamine and electroneutral halogenated aryl hydrocarbon (Kosugi, M.; Kameyama, M.; Migita, T.Chem.Lett.1983,927-928.).In the eighties of last century the nineties, two research groups of Hartwig and Buchwald almost simultaneously to this type reaction further investigate, improve and developed the catalystsystem that is applicable to such reaction in a large number.Over past ten years, plurality of ligands such as organophosphorus ligand, nitrogen heterocycle carbine ligand, phosphine oxide part etc. are designed and synthesize, and the amination reaction that is applied to the catalytic halogenated aryl hydrocarbon of palladium has been obtained good catalytic effect.Especially Nolan etc. has developed the palladium metal mixture of a large amount of nitrogen heterocyclic ring carbenes, and these compounds have shown the catalytic performance more superior than organophosphorus ligand (Diez-Gonzalez, S. in the amination reaction of halogenated aryl hydrocarbon; Marion, N.; Nolan, S.P.Chem.Rev.2009,109,3612-3676; Marion, N.; Nolan, S.P.Acc.Chem.Res.2008,41,1440-1449; Diez-Gonzalez, S.; Nolan, S.P.Coord.Chem.Rev.2007,251,874-883.).Deep research shows, except nitrogen heterocycle carbine ligand, other part that is centered around the former subcenter of palladium metal also has remarkable influence to their catalytic activity.For example, Organ etc. have developed one type of N-heterocyclic carbine metal palladium mixture that contains pyridine, discover that the wherein substituent space of pyridine and electronic effect have significant effects (Nasielski, J. to the catalytic performance of this compounds; Hadei, N.; Achonduh, G.; Kantchev, E.A.B.; O ' Brien, C.J.; Lough, A.; Organ, M.G.Chem.Eur.J.2010,16,10844-10853.).In addition, although the palladium metal mixture of existing a large amount of nitrogen heterocyclic ring carbenes is synthesized out at present, yet still lack general and effective catalyzer for the cross-coupling reaction that has than large space sterically hindered halogenated aryl hydrocarbon and organic amine.Therefore exploitation nitrogen heterocycle carbine ligand palladium catalyst more efficiently, and be applied to this type and have good application prospect and have in the very big challenging reaction, important practical value had.
Summary of the invention
The object of the invention aims to provide a kind of pyridine-2-formate or pyridine-2 of containing, N-heterocyclic carbine palladium mixture and the preparation and the application of the two formate parts of 6-.Contain pyridine-2-formate or pyridine-2; The N-heterocyclic carbine palladium mixture of the two formate parts of 6-has very high catalytic activity as a kind of catalyst applications in the C-N of halogenated aryl hydrocarbon and organic amine cross-coupling reaction, for synthesize substituted arylamine provide a kind of more efficiently, method more easily.
Pyridine-2-formate or the pyridine-2 of containing provided by the invention, the N-heterocyclic carbine palladium mixture of the two formate parts of 6-has the compound of following chemical structure of general formula:
Wherein: m=0～4; N=0～3;
R
1, R
2Be respectively C
1～C
10One, two, three alkyl, C
5～C
10Naphthenic base, 1-adamantyl, 2-adamantyl, phenyl, C
1～C
10The substituted phenyl of alkyl, C
1～C
10The substituted phenyl of alkoxyl group; R
1And R
2Can be identical, also can be different;
R
3, R
4Be respectively H, C
1～C
10Alkyl, phenyl, C
1～C
8Substituted phenyl of alkyl or R
3～R
4For and alicyclic ring or aromatic ring; R
3, R
4Can be identical, also can be different; R
5Be H, C
1～C
10Alkyl, C
1～C
10Alkoxyl group, phenyl, C
1～C
10The substituted phenyl of alkyl, C
1～C
10The substituted phenyl of alkoxyl group.
In the described N-heterocyclic carbine palladium mixture, on the unsaturated nitrogen heterocycle 4,5-bit substituent R
3, R
4Part, it comprises racemic modification, dextrorotatory form and the levo form that has identical chemical structure of general formula but have different three-dimensional arrangements and rotary light performance:
Alternatively, in the described N-heterocyclic carbine palladium mixture, C
1～C
10Alkyl is methyl, ethyl, n-propyl, sec.-propyl, cyclopropyl, normal-butyl, isobutyl-, sec.-butyl, the tertiary butyl, cyclobutyl, n-pentyl, isopentyl, neo-pentyl, sec.-amyl sec-pentyl secondary amyl, tert-pentyl, cyclopentyl, n-hexyl, isohexyl, new hexyl, Sec-Hexyl, uncle's hexyl, cyclohexyl, n-heptyl, different heptyl, new heptyl, Zhong Gengji, uncle's heptyl, suberyl, n-octyl, iso-octyl, new octyl group, secondary octyl, uncle's octyl group or ring octyl group; C
1～C
10Alkoxyl group is a methoxyl group; Oxyethyl group; Positive propoxy; Isopropoxy; The ring propoxy-; N-butoxy; Isobutoxy; Sec.-butoxy; Tert.-butoxy; Cyclobutoxy group; N-pentyloxy; Isopentyloxy; Neopentyl oxygen; Secondary pentyloxy; Uncle's pentyloxy; Cyclopentyloxy; Positive hexyloxy; Different hexyloxy; New hexyloxy; Secondary hexyloxy; Uncle's hexyloxy; Cyclohexyloxy; Positive heptan the oxygen base; Different heptan the oxygen base; New heptan the oxygen base; Zhong Geng oxygen base; Uncle's oxygen in heptan base; Ring oxygen base in heptan; N-octyloxy; Different octyloxy; New octyloxy; Secondary octyloxy; Uncle's octyloxy or ring octyloxy.
The invention discloses and contain pyridine-2-formate or pyridine-2, the compound method of the N-heterocyclic carbine palladium mixture of the two formate parts of 6-, its building-up process can be represented with following reaction formula:
Wherein: m=0～4, n=0～3; R
1, R
2, R
3, R
4, R
5Value such as claim 1 definition; X is chlorine, hexafluoro-phosphate radical or tetrafluoroborate.
Concrete step: with corresponding imidazoles or imidazoline salt; Palladous chloride and 2-VPP or 2, dipicolimic acid 2 are starting raw material, under salt of wormwood or cesium carbonate effect; Under 90～100 ℃ of temperature; In organic solvent one pot reaction 12-24 hour, generate and contain pyridine-2-formate or pyridine-2, the N-heterocyclic carbine palladium mixture of the two formate parts of 6-; Imidazoles or imidazoline salt, palladium chloride and 2-VPP or 2, the mol ratio of dipicolimic acid 2 are 1.2: 1: 1.1; Solvent is preferred 1,4-dioxane, glycol dimethyl ether, N, one or more in the dinethylformamide.
The invention also discloses and contain pyridine-2-formate or pyridine-2, the another kind of compound method of the N-heterocyclic carbine palladium mixture of the two formate parts of 6-:
Wherein: m=0～4, n=0～3; R
1, R
2, R
3, R
4, R
5Value such as claim 1 definition.
Concrete implementation step: with corresponding N-heterocyclic carbine Palladous chloride dimer and 2-VPP or 2; Dipicolimic acid 2 is a starting raw material; Under salt of wormwood or cesium carbonate effect, under 90～100 ℃ of temperature, reaction is 10-12 hour in organic solvent; Generation contains pyridine-2-formate or pyridine-2, the N-heterocyclic carbine palladium mixture of the two formate parts of 6-; N-heterocyclic carbine palladium chloride dimer and 2-VPP or 2, the mol ratio of dipicolimic acid 2 are 1: 2.0～3.0; Solvent is preferred 1,4-dioxane, glycol dimethyl ether, N, one or more in the dinethylformamide.
The invention also discloses and contain pyridine-2-formate or pyridine-2, the N-heterocyclic carbine palladium mixture of the two formate parts of 6-is used for the C-N cross-coupling reaction of halogenated aryl hydrocarbon and organic amine as catalyzer in the presence of alkali, and catalyst levels is 1～3mol%; Solvent is 1, one or more in 4-dioxane, glycol dimethyl ether or the toluene; Temperature of reaction is 80～100 ℃; Reaction times is 10 minutes～120 minutes, and its reaction formula is:
Wherein: [Pd] is N-heterocyclic carbine palladium complex catalyst of the present invention; X is halogen atom chlorine, bromine, iodine; R
6, R
7, R
8, R
9, R
10Be respectively H, C
1～C
10Alkyl, benzyl, styroyl, phenyl, C
1～C
10The substituted phenyl of alkyl, C
1～C
10The substituted phenyl of alkoxyl group, naphthyl, furyl, thienyl, pyridyl; R
6, R
7, R
8, R
9, R
10Can be identical, also can be different.R
11, R
12Be respectively C
1～C
10Alkyl, benzyl, phenyl, C
1～C
10The substituted phenyl of alkyl, C
1～C
10The substituted phenyl of alkoxyl group, naphthyl, furyl, thienyl, pyridyl; R
11, R
12Can be identical, also can be different.
The C-N cross-coupling reaction of catalytic halogenated aryl hydrocarbon of palladium according to the invention and organic amine is under nitrogen or argon shield; In organic solvent (as 1,4-dioxane, glycol dimethyl ether, N, one or more in dinethylformamide or the toluene); Employing contains pyridine-2-formate or pyridine-2 with respect to halogenated aryl hydrocarbon 1～3mol%'s; The N-heterocyclic carbine palladium mixture of the two formate parts of 6-adds halogenated aryl hydrocarbon and organic amine (mol ratio of halogenated aryl hydrocarbon and organic amine is 1: 1.1) successively as catalyzer, keeps temperature of reaction at 90～100 ℃; Stirring reaction 10～120 minutes can obtain the aromatic amine product of high yield.
Pyridine-2-formate or the pyridine-2 of containing of the present invention; The N-heterocyclic carbine palladium mixture of the two formate parts of 6-has very high activity for the cross-coupling with sterically hindered halogenated aryl hydrocarbon and organic amine substrate; Can be used for blended space crowded substituted aromatic amine of N-alkyl and diarylamine compound, be one of catalyzer the most efficiently in the catalytic C-N cross-coupling reaction of present palladium.
Embodiment
To help further to understand the present invention through following embodiment, but not limit content of the present invention.Preparing method of the present invention can be further embodies as follows with the preparation process of representation compound:
Embodiment 1: N-heterocyclic carbine pyridine-2-carboxylic acids Palladous chloride (IPr) Pd (Py-2-caboxylate) Cl
Induction stirring is being housed, and the head of bleeding adds 1 in the exsiccant 250mL there-necked flask of reflux condensing tube and anti-mouthful of plug; 3-pair-(2 ', 6 '-diisopropyl phenyl)-imidazole hydrochloride (IPrHCl) (527mg, 1.1mmol); Palladous chloride (177mg, 1.0mmol), cesium carbonate (1630mg; 5.0mmol) and the 2-VPP (136mg 1.1mmol), is replaced into nitrogen atmosphere with system.In this system, add and newly steam 1,4-dioxane (20mL), 100 ℃ of following stirring reactions 12 hours; Through diatomite filtration and with methylene dichloride (20mL) washing filter residue, merging filtrate revolves the resistates that obtains behind the steaming precipitation through purification by silica gel column chromatography; Get yellow solid, yield 60%.Fusing point:＞280 ℃.
1H?NMR(400MHz，CDCl
3)：δ8.55(d，1H)，7.80(t，2H)，7.49(t，2H)，7.34(m，5H)，7.18(s，2H)，2.95(m，4H)，1.41(d，12H)，1.13(d，12H)。
13C?NMR(75MHz，CDCl
3)：δ172.8，157.2，151.2，146.8，146.5，139.2，134.5，130.4，126.7，126.2，125.2，124.1，28.6，26.2，22.9。
Embodiment 2: N-heterocyclic carbine pyridine-2-carboxylic acids Palladous chloride (SIPr) Pd (Py-2-caboxylate) Cl
Compound method is with embodiment 1, and with 1,3-is two-(2 ', 6 '-diisopropyl phenyl)-tetrahydroglyoxaline a tetrafluoro borate (SIPrHBF
4) replace 1,3-pair-(2 ', 6 '-diisopropyl phenyl)-imidazole hydrochloride (IPrHCl).Product is a yellow solid, yield 56%.Fusing point:＞280 ℃.
1H?NMR(400MHz，CDCl
3)：δ8.51(d，1H)，7.78(t，2H)，7.40(t，2H)，7.28(m，5H)，4.11(s，4H)，3.44(m，4H)，1.40(d，12H)，1.12(d，12H)。
13C?NMR(75MHz，CDCl
3)：δ187.6，172.7，151.2，147.7，146.4，139.2，134.6，129.6，126.6，126.2，124.5，53.7，28.7，26.6，23.8。
Embodiment 3: N-heterocyclic carbine pyridine-2,6-dicarboxylicacid palladium (IPr) Pd (Py-2,6-dicaboxylate)
Compound method is with embodiment 1, and with 2, the 6-dinicotinic acid replaces the 2-VPP.Product is a yellow solid, yield 44%.Fusing point:＞280 ℃.
1H?NMR(400MHz，CDCl
3)：δ7.95(t，1H)，7.70(d，2H)，7.51(t，2H)，7.36(m，4H)，7.22(s，2H)，2.70(m，4H)，1.39(d，12H)，1.16(d，12H)。
13C?NMR(75MHz，CDCl
3)：δ171.9，164.0，147.9，146.6，140.4，134.1，130.5，127.0，125.2，124.2，28.7，25.6，23.1。
Embodiment 4: N-heterocyclic carbine pyridine-2,6-dicarboxylicacid palladium (SIPr) Pd (Py-2,6-dicaboxylate)
Compound method is with embodiment 2, and with 2, the 6-dinicotinic acid replaces the 2-VPP.Product is a yellow solid, yield 39%.Fusing point:＞280 ℃.
1H?NMR(400MHz，CDCl
3)：δ7.93(t，1H)，7.70(d，2H)，7.43(t，2H)，7.30(m，4H)，4.13(s，4H)，3.23(m，4H)，1.44(d，12H)，1.30(d，12H)。
13C?NMR(75MHz，CDCl
3)：δ192.9，171.9，147.7，140.4，134.0，130.0，127.0，124.7，53.9，28.8，26.0，23.9。
Embodiment 5: N-heterocyclic carbine pyridine-2-carboxylic acids Palladous chloride (IPr) Pd (Py-2-caboxylate) Cl
Induction stirring is being housed, and the head of bleeding adds N-heterocyclic carbine Palladous chloride dimer ([(IPr) PdCl in the exsiccant 250mL there-necked flask of reflux condensing tube and anti-mouthful of plug
2]
2) (527mg, 1.1mmol), (1630mg, 5.0mmol) (136mg 1.1mmol), is replaced into nitrogen atmosphere with system to cesium carbonate with the 2-VPP.In this system, add and newly steam 1,4-dioxane (20mL), 100 ℃ of following stirring reactions 12 hours; Through diatomite filtration and with methylene dichloride (20mL) washing filter residue, merging filtrate revolves the resistates that obtains behind the steaming precipitation through purification by silica gel column chromatography; Get yellow solid, yield 90%.Its physical constant characterizes with embodiment 1.
Embodiment 6: N-heterocyclic carbine pyridine-2-carboxylic acids Palladous chloride (SIPr) Pd (Py-2-caboxylate) Cl
Compound method is with embodiment 5, with N-heterocyclic carbine Palladous chloride dimer ([(SIPr) PdCl
2]
2) replacement N-heterocyclic carbine Palladous chloride dimer ([(IPr) PdCl
2]
2).Product is a yellow solid, yield 86%.Its physical constant characterizes with embodiment 2.
Embodiment 7: N-heterocyclic carbine pyridine-2,6-dicarboxylicacid palladium (IPr) Pd (Py-2,6-dicaboxylate)
Compound method is with embodiment 5, and with 2, the 6-dinicotinic acid replaces the 2-VPP.Product is a yellow solid, yield 85%.Its physical constant characterizes with embodiment 3.
Embodiment 8: N-heterocyclic carbine pyridine-2,6-dicarboxylicacid palladium (SIPr) Pd (Py-2,6-dicaboxylate)
Compound method is with embodiment 6, and with 2, the 6-dinicotinic acid replaces the 2-VPP.Product is a yellow solid, yield 83%.Its physical constant characterizes with embodiment 4.
Embodiment 9: the C-N cross-coupling reaction of catalytic halogenated aryl hydrocarbon of palladium and organic amine
Under argon atmosphere, in exsiccant Schlenk bottle, add N-heterocyclic carbine pyridine-2,6-carboxylic acid palladium ((IPr) Pd (Py-2; 6-dicarboxylate)) (6.6mg, 0.01mmol), sodium tert-butoxide (144mg; 1.5mmol); Halogenated aryl hydrocarbon (1mmol), organic amine (1.1mmol) and 3mL 1,4-dioxane.With reaction soln in 100 ℃ of following stirring reaction 10-120 minutes.Product is through purification by silica gel column chromatography, and petrol ether/ethyl acetate (20: 1) is as eluent, and yield results is seen table 1.Table 1 is the C-N cross-coupling reaction result of catalytic halogenated aryl hydrocarbon of palladium and organic amine.
Table 1
| Entry | R 6 | R 7 | R 8 | R 9 | R 10 | R 11 | R 12 | Yield(％) |
| 1 | Me | H | H | H | H | n-Bu | n-Bu | 97 |
| 2 | Me | H | H | H | H | H | Mes | 99 |
| 3 | MeO | H | H | H | H | H | Mes | 98 |
| 4 | Me | H | H | H | Me | n-Bu | n-Bu | 97 |
| 5 | Me | H | H | H | Me | H | n-Decanyl | 98 |
| 6 | Me | H | H | H | Me | H | Ph | 97 |
| 7 | Me | H | H | H | Me | H | o-Tol | 98 |
| 8 | Me | H | H | H | Me | H | 1-Naphthyl | 99 |
| 9 | Me | H | H | H | Me | H | 2-Naphthyl | 98 |
| 10 | Me | H | H | H | Me | H | Cy | 95 |
| 11 | Me | H | Me | H | Me | H | Mes | 97 |
| 12 | Me | H | Me | H | Me | H | 2，6-Et 2Ph | 97 |
| 13 | Me | H | Me | H | Me | H | 2，6- iPr 2Ph | 96 |
| 14 | Me | H | Me | H | Me | n-Bu | n-Bu | 98 |
| 15 | Me | H | Me | H | Me | Cy | Cy | 96 |
| 16 | Et | H | H | H | Et | H | Mes | 98 |
| 17 | Et | H | H | H | Et | H | 2，6-Et 2Ph | 96 |
| 18 | Et | H | H | H | Et | H | 2，6- iPr 2Ph | 96 |
| 19 | Et | H | H | H | Et | H | n-Decanyl | 98 |
| 20 | Et | H | H | H | Et | n-Bu | n-Bu | 96 |
| 21 | iPr | H | H | H | iPr | H | Mes | 97 |
| 22 | iPr | H | H | H | iPr | H | n-Decanyl | 94 |
| 23 | iPr | H | H | H | iPr | H | 2，6-Et 2Ph | 90 |
| 24 | iPr | H | H | H | iPr | H | 2，6- iPr 2Ph | 54 |
Claims (10)
1. one kind contains pyridine-2-formate or pyridine-2, and the N-heterocyclic carbine palladium mixture of the two formate parts of 6-is characterized in that having following structural formula:
Wherein: m=0～4; N=0～3;
R
1, R
2Be respectively C
1～C
10One, two, three alkyl, C
5～C
10Naphthenic base, 1-adamantyl, 2-adamantyl, phenyl, C
1～C
10The substituted phenyl of alkyl, C
1～C
10The substituted phenyl of alkoxyl group; R
1And R
2Can be identical, also can be different;
R
3, R
4Be respectively H, C
1～C
10Alkyl, phenyl, C
1～C
8Substituted phenyl of alkyl or R
3～R
4For and alicyclic ring or aromatic ring; R
3, R
4Can be identical, also can be different;
R
5Be H, C
1～C
10Alkyl, C
1～C
10Alkoxyl group, phenyl, C
1～C
10The substituted phenyl of alkyl, C
1～C
10The substituted phenyl of alkoxyl group.
2. according to the described N-heterocyclic carbine palladium of claim 1 mixture, it is characterized in that on the unsaturated nitrogen heterocycle 4 5-bit substituent R
3, R
4Part, it comprises racemic modification, dextrorotatory form and the levo form that has identical chemical structure of general formula but have different three-dimensional arrangements and rotary light performance:
3. according to the described N-heterocyclic carbine palladium of claim 1 mixture, it is characterized in that described C
1～C
10Alkyl is methyl, ethyl, n-propyl, sec.-propyl, cyclopropyl, normal-butyl, isobutyl-, sec.-butyl, the tertiary butyl, cyclobutyl, n-pentyl, isopentyl, neo-pentyl, sec.-amyl sec-pentyl secondary amyl, tert-pentyl, cyclopentyl, n-hexyl, isohexyl, new hexyl, Sec-Hexyl, uncle's hexyl, cyclohexyl, n-heptyl, different heptyl, new heptyl, Zhong Gengji, uncle's heptyl, suberyl, n-octyl, iso-octyl, new octyl group, secondary octyl, uncle's octyl group or ring octyl group; C
1～C
10Alkoxyl group is a methoxyl group; Oxyethyl group; Positive propoxy; Isopropoxy; The ring propoxy-; N-butoxy; Isobutoxy; Sec.-butoxy; Tert.-butoxy; Cyclobutoxy group; N-pentyloxy; Isopentyloxy; Neopentyl oxygen; Secondary pentyloxy; Uncle's pentyloxy; Cyclopentyloxy; Positive hexyloxy; Different hexyloxy; New hexyloxy; Secondary hexyloxy; Uncle's hexyloxy; Cyclohexyloxy; Positive heptan the oxygen base; Different heptan the oxygen base; New heptan the oxygen base; Zhong Geng oxygen base; Uncle's oxygen in heptan base; Ring oxygen base in heptan; N-octyloxy; Different octyloxy; New octyloxy; Secondary octyloxy; Uncle's octyloxy or ring octyloxy.
4. according to the described N-heterocyclic carbine palladium of claim 1 mixture, it is characterized in that it has following structural formula:
5. according to the described N-heterocyclic carbine palladium of claim 1 mixture, it is characterized in that it has following structural formula:
6. according to the described N-heterocyclic carbine palladium of claim 2 mixture, it is characterized in that it has following structural formula:
7. the preparation method of claim 1 or 2 described N-heterocyclic carbine palladium mixtures is characterized in that the step that comprises: with corresponding imidazoles or imidazoline salt, and Palladous chloride and 2-VPP or 2; Dipicolimic acid 2 is a starting raw material; Under salt of wormwood or cesium carbonate effect, under 90～100 ℃ of temperature, reaction is 12-24 hour in organic solvent; Generation contains pyridine-2-formate or pyridine-2, the N-heterocyclic carbine palladium mixture of the two formate parts of 6-; Imidazoles or imidazoline salt, palladium chloride and 2-VPP or 2, the mol ratio of dipicolimic acid 2 are 1.2: 1: 1.1; Solvent is 1,4-dioxane, glycol dimethyl ether, N, and at least a in the dinethylformamide:
Wherein: m=0～4, n=0～3; R
1, R
2, R
3, R
4, R
5Value such as claim 1 definition; X is chlorine, hexafluoro-phosphate radical or tetrafluoroborate.
8. the preparation method of claim 1 or 2 described N-heterocyclic carbine palladium mixtures; It is characterized in that the step that comprises: with corresponding N-heterocyclic carbine Palladous chloride dimer and 2-VPP or 2, dipicolimic acid 2 is a starting raw material, under salt of wormwood or cesium carbonate effect; Under 90～100 ℃ of temperature; Reaction is 10-12 hour in organic solvent, generates to contain pyridine-2-formate or pyridine-2 the N-heterocyclic carbine palladium mixture of the two formate parts of 6-; N-heterocyclic carbine palladium chloride dimer and 2-VPP or 2, the mol ratio of dipicolimic acid 2 are 1: 2.0～3.0; Solvent is selected from 1,4-dioxane, glycol dimethyl ether, N, and one or more in the dinethylformamide::
Wherein: m=0～4, n=0～3; R
1, R
2, R
3, R
4, R
5Value such as claim 1 definition.
9. the application of the arbitrary described N-heterocyclic carbine palladium mixture of claim 1-6 is characterized in that this compound is used for the C-N cross-coupling reaction of halogenated aryl hydrocarbon and organic amine as catalyzer in the presence of alkali.
10. according to the application of the described N-heterocyclic carbine palladium of claim 9 mixture, it is characterized in that comprising following step:
In the solvent in the presence of argon gas or nitrogen atmosphere and N-heterocyclic carbine palladium complex catalyst, halogenated aryl hydrocarbon and organic amine stirring reaction 10 minutes～120 minutes, product is through purification by silica gel column chromatography, and petrol ether/ethyl acetate (20: 1) is as eluent; Catalyst levels is 1～3mol%, and the mol ratio of halogenated aryl hydrocarbon and organic amine is 1: 1.1, and temperature of reaction is at 90～100 ℃; Solvent is 1, one or more in 4-dioxane, glycol dimethyl ether or the toluene; Its reaction formula is:
Wherein: X is halogen atom chlorine, bromine, iodine; R
6, R
7, R
8, R
9, R
10Be respectively H, C
1～C
10Alkyl, benzyl, styroyl, phenyl, C
1～C
10The substituted phenyl of alkyl, C
1～C
10The substituted phenyl of alkoxyl group, naphthyl, furyl, thienyl, pyridyl; R
6, R
7, R
8, R
9, R
10Can be identical, also can be different; R
11, R
12Be respectively C
1～C
10Alkyl, naphthenic base, benzyl, phenyl, C
1～C
10The substituted phenyl of alkyl, C
1～C
10The substituted phenyl of alkoxyl group, naphthyl, furyl, thienyl, pyridyl; R
11, R
12Can be identical, also can be different.
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