CN102627672B - 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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- CN102627672B CN102627672B CN201210077288.3A CN201210077288A CN102627672B CN 102627672 B CN102627672 B CN 102627672B CN 201210077288 A CN201210077288 A CN 201210077288A CN 102627672 B CN102627672 B CN 102627672B
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- 0 *c1c(*)c(*)c(*)c(*)c1* Chemical compound *c1c(*)c(*)c(*)c(*)c1* 0.000 description 3
- WJJMNDUMQPNECX-UHFFFAOYSA-N OC(c1nc(C(O)=O)ccc1)=O Chemical compound OC(c1nc(C(O)=O)ccc1)=O WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 1
- SIOXPEMLGUPBBT-UHFFFAOYSA-N OC(c1ncccc1)=O Chemical compound OC(c1ncccc1)=O SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 1
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 N-heterocyclic carbine palladium mixture containing pyridine-2-formate or the two formate parts of pyridine-2,6-and preparation method and application thereof.This N-heterocyclic carbine palladium mixture can be used as catalyzer in the C-N cross-coupling reaction of halogenated aryl hydrocarbon and organic amine, has very high catalytic activity.Especially have high activity to the C-N cross-coupling reaction of the chlorinated aromatic hydrocarbons and organic amine with larger space steric hindrance, this is one of the most efficient catalyzer in transition metal-catalyzed at present C-N cross-coupling reaction.
Background technology
Aromatic amine compounds, according to its constitutional features, is widely used in pharmacy, optics and electricity material and the purposes such as part as transition metal ion.Although aromatic amine compounds structure is simple, its synthesis is usually more difficult.General needs are nitrated, reduction, and the existence of some functional group also can hinder substitution reaction; Reductive amination method is applicable to the arylamine preparing the replacement of some alkyl, 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 adopt the halogenated aryl hydrocarbon of activation.Although adopt the Ullmann of traditional copper catalysis reaction also can carry out substitution reaction, but reaction needs could occur under the condition heated up usually, and the existence of susceptible functionality is also unfavorable for the carrying out of reaction.In addition, often can there is diarylide reaction in the uncle's arylamine adopting the method to obtain, generate by product.Therefore, the C-N cross-coupling reaction synthetic aroma aminated compounds of research and development novel transition metal catalysis is focus (the Ackermann L. Ed.Modern Arylation Methods in Synthetic Organic Chemistry research field all the time, Wiley-VCH:Weinheim, Germany, 2009).Compared with traditional catalysed reaction of copper, transition metal palladium, nickel etc. have the advantages such as more efficient, the substrate scope of application is wider as catalyst application in C-N binding reaction.As far back as nineteen eighty-three, Migita etc. report the amino tin of tributyl and aryl bromide reaction can prepare aromatic amine compound under palladium chtalyst, and this reaction is applicable to dialkylamine and electroneutral halogenated aryl hydrocarbon (Kosugi, M.; Kameyama, M.; Migita, T.Chem.Lett.1983,927-928.).In eighties of last century the nineties, Hartwig and Buchwald Liang Ge research group almost conducts in-depth research the reaction of this class simultaneously, improves and has developed the catalyst system being applicable to such reaction in a large number.Nearly ten years, a large amount of part such as organophosphorus ligand, nitrogen heterocycle carbine ligand, Phosphine Oxide Ligands etc. are designed and synthesize, and the amination reaction being applied to the halogenated aryl hydrocarbon of palladium chtalyst achieves good catalytic effect.Especially Nolan etc. have developed the palladium metal mixture of a large amount of nitrogen heterocyclic ring carbenes, and these compounds show catalytic performance (Diez-Gonzalez, the S. more superior than organophosphorus ligand 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 being centered around palladium metal atom center also has significant impact to their catalytic activity.Such as, Organ etc. have developed the N-heterocyclic carbine metal palladium mixture of a class containing pyridine, and research finds that the space of wherein pyridine substituents and the catalytic performance of electronic effect on this compounds have important impact (Nasielski, J.; 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 at present the palladium metal mixture of existing a large amount of nitrogen heterocyclic ring carbenes is synthesized out, but general and effective catalyzer is still lacked for the cross-coupling reaction of the halogenated aryl hydrocarbon and organic amine with larger space steric hindrance.Therefore develop nitrogen heterocycle carbine ligand palladium catalyst more efficiently, and be applied to this kind ofly to there is good application prospect and have in very large challenging reaction, there is important practical value.
Summary of the invention
Object of the present invention aims to provide a kind of the N-heterocyclic carbine palladium mixture and the preparations and applicatio that contain pyridine-2-formate or the two formate parts of pyridine-2,6-.Containing pyridine-2-formate or pyridine-2, the N-heterocyclic carbine palladium mixture of the two formate part of 6-has very high catalytic activity as a kind of catalyst application in the C-N cross-coupling reaction of halogenated aryl hydrocarbon with organic amine, the arylamine for synthesis replacement provide one more efficiently, method more easily.
The N-heterocyclic carbine palladium mixture containing pyridine-2-formate or the two formate parts of pyridine-2,6-provided by the invention 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
10cycloalkyl, 1-adamantyl, 2-adamantyl, phenyl, C
1~ C
10phenyl, C that alkyl replaces
1~ C
10the phenyl that alkoxyl group replaces; R
1and R
2can be identical, also can be different;
R
3, R
4be respectively H, C
1~ C
10alkyl, phenyl, C
1~ C
8the phenyl that alkyl replaces or R
3~ R
4for and alicyclic ring or aromatic ring; R
3, R
4can be identical, also can be different; R
5for H, C
1~ C
10alkyl, C
1~ C
10alkoxyl group, phenyl, C
1~ C
10phenyl, C that alkyl replaces
1~ C
10the phenyl that alkoxyl group replaces.
In described N-heterocyclic carbine palladium mixture, for 4,5-bit substituent R on unsaturated nitrogen heterocycle
3, R
4part, it comprises and has identical chemical structure of general formula but have the racemic modification of different three-dimensional arrangements and rotary light performance, dextrorotatory form and levo form:
Alternatively, in 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, tertiary hexyl, cyclohexyl, n-heptyl, different heptyl, new heptyl, Zhong Gengji, tertiary heptyl, suberyl, n-octyl, iso-octyl, new octyl group, secondary octyl, tertiary octyl group or ring octyl group, C
1~ C
10alkoxyl group is methoxyl group, oxyethyl group, positive propoxy, isopropoxy, ring propoxy-, n-butoxy, isobutoxy, sec-butoxy, tert.-butoxy, cyclobutoxy group, n-pentyloxy, isopentyloxy, neopentyl oxygen, secondary pentyloxy, tertiary pentyloxy, cyclopentyloxy, positive hexyloxy, different hexyloxy, new hexyloxy, secondary hexyloxy, tertiary hexyloxy, cyclohexyloxy, positive heptan oxygen base, different heptan oxygen base, new heptan oxygen base, Zhong Geng oxygen base, tertiary heptan oxygen base, ring oxygen in heptan base, n-octyloxy, different octyloxy, new octyloxy, secondary octyloxy, tertiary octyloxy or ring octyloxy.
The invention discloses the synthetic method of the N-heterocyclic carbine palladium mixture containing pyridine-2-formate or the two formate parts of pyridine-2,6-, its building-up process can represent with reaction formula below:
Wherein: m=0 ~ 4, n=0 ~ 3; R
1, R
2, R
3, R
4, R
5value as claim 1 define; X is chlorine, hexafluoro-phosphate radical or tetrafluoroborate.
Concrete step: with corresponding imidazoles or imidazoline salt, Palladous chloride and 2-pyridine carboxylic acid or 2, dipicolimic acid 2 is starting raw material, under salt of wormwood or cesium carbonate effect, at 90 ~ 100 DEG C of temperature, one pot reaction 12-24 hour in organic solvent, generates the N-heterocyclic carbine palladium mixture containing pyridine-2-formate or the two formate part of pyridine-2,6-; Imidazoles or imidazoline salt, palladium chloride and 2-pyridine carboxylic acid or 2, the mol ratio of dipicolimic acid 2 is 1.2: 1: 1.1; One or more in the preferred Isosorbide-5-Nitrae-dioxane of solvent, glycol dimethyl ether, DMF.
The invention also discloses the another kind of synthetic method of the N-heterocyclic carbine palladium mixture containing pyridine-2-formate or the two formate parts of pyridine-2,6-:
Wherein: m=0 ~ 4, n=0 ~ 3; R
1, R
2, R
3, R
4, R
5value as claim 1 define.
Concrete implementation step: with corresponding N-heterocyclic carbine Palladous chloride dimer and 2-pyridine carboxylic acid or 2, dipicolimic acid 2 is starting raw material, under salt of wormwood or cesium carbonate effect, at 90 ~ 100 DEG C of temperature, react 10-12 hour in organic solvent, generate the N-heterocyclic carbine palladium mixture containing pyridine-2-formate or the two formate part of pyridine-2,6-; N-heterocyclic carbine palladium chloride dimer and 2-pyridine carboxylic acid or 2, the mol ratio of dipicolimic acid 2 is 1: 2.0 ~ 3.0; One or more in the preferred Isosorbide-5-Nitrae-dioxane of solvent, glycol dimethyl ether, DMF.
The invention also discloses N-heterocyclic carbine palladium mixture containing pyridine-2-formate or the two formate parts of pyridine-2,6-as catalyzer in the presence of a base for the C-N cross-coupling reaction of halogenated aryl hydrocarbon and organic amine, catalyst levels is 1 ~ 3mol%; Solvent is one or more in Isosorbide-5-Nitrae-dioxane, glycol dimethyl ether or toluene; Temperature of reaction is 80 ~ 100 DEG C; 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
10phenyl, C that alkyl replaces
1~ C
10phenyl, naphthyl, furyl, thienyl, pyridyl that alkoxyl group replaces; 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
10phenyl, C that alkyl replaces
1~ C
10phenyl, naphthyl, furyl, thienyl, pyridyl that alkoxyl group replaces; R
11, R
12can be identical, also can be different.
The halogenated aryl hydrocarbon of palladium chtalyst of the present invention and the C-N cross-coupling reaction of organic amine are under nitrogen or argon, at organic solvent (as 1, 4-dioxane, glycol dimethyl ether, N, one or more in dinethylformamide or toluene) in, adopt relative to halogenated aryl hydrocarbon 1 ~ 3mol% containing pyridine-2-formate or pyridine-2, the N-heterocyclic carbine palladium mixture of the two formate part of 6-is as catalyzer, add halogenated aryl hydrocarbon and organic amine (mol ratio of halogenated aryl hydrocarbon and organic amine is 1: 1.1) successively, keep temperature of reaction at 90 ~ 100 DEG C, stirring reaction 10 ~ 120 minutes, the aromatic amine product of high yield can be obtained.
Of the present invention containing pyridine-2-formate or pyridine-2, the N-heterocyclic carbine palladium mixture of the two formate part of 6-has very high activity for the cross-coupling with sterically hindered halogenated aryl hydrocarbon and organic amine substrate, can be used for aromatic amine that the crowded N-alkyl of blended space replaces and diaromatic amine compound, be one of the most efficient catalyzer in the C-N cross-coupling reaction of current palladium chtalyst.
Embodiment
To contribute to understanding the present invention further by following embodiment, but not limit content of the present invention.Preparation method of the present invention can embody as follows by the preparation process of representation compound further:
Embodiment 1: N-heterocyclic carbine pyridine-2-carboxylic acids Palladous chloride (IPr) Pd (Py-2-caboxylate) Cl
Induction stirring is being housed, air exhaust head, adds 1,3-two-(2 ' in the 250mL there-necked flask of the drying of reflux condensing tube and anti-mouth plug, 6 '-diisopropyl phenyl)-imidazole hydrochloride (IPrHCl) (527mg, 1.1mmol), Palladous chloride (177mg, 1.0mmol), cesium carbonate (1630mg, 5.0mmol) with 2-pyridine carboxylic acid (136mg, 1.1mmol), system is replaced into nitrogen atmosphere.New steaming 1 is added in this system, 4-dioxane (20mL), stirring reaction 12 hours at 100 DEG C, also filter residue is washed with methylene dichloride (20mL) through diatomite filtration, merging filtrate, revolve the residue by silicagel column chromatography purification obtained after steaming precipitation, obtain yellow solid, yield 60%.Fusing point: > 280 DEG C.
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
Synthetic method with embodiment 1, with 1,3-two-(2 ', 6 '-diisopropyl phenyl)-tetrahydroglyoxaline a tetrafluoro borate (SIPrHBF
4) replace 1,3-pair-(2 ', 6 '-diisopropyl phenyl)-imidazole hydrochloride (IPrHCl).Product is yellow solid, yield 56%.Fusing point: > 280 DEG C.
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-dicarboxylic acid palladium (IPr) Pd (Py-2,6-dicaboxylate)
Synthetic method, with embodiment 1, replaces 2-pyridine carboxylic acid with 2,6-dinicotinic acid.Product is yellow solid, yield 44%.Fusing point: > 280 DEG C.
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-dicarboxylic acid palladium (SIPr) Pd (Py-2,6-dicaboxylate)
Synthetic method, with embodiment 2, replaces 2-pyridine carboxylic acid with 2,6-dinicotinic acid.Product is yellow solid, yield 39%.Fusing point: > 280 DEG C.
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, air exhaust head, in the 250mL there-necked flask of the drying of reflux condensing tube and anti-mouth plug, is adding N-heterocyclic carbine Palladous chloride dimer ([(IPr) PdCl
2]
2) (527mg, 1.1mmol), cesium carbonate (1630mg, 5.0mmol) and 2-pyridine carboxylic acid (136mg, 1.1mmol), be replaced into nitrogen atmosphere by system.New steaming 1 is added in this system, 4-dioxane (20mL), stirring reaction 12 hours at 100 DEG C, also filter residue is washed with methylene dichloride (20mL) through diatomite filtration, merging filtrate, revolve the residue by silicagel column chromatography purification obtained after steaming precipitation, obtain 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
Synthetic method with embodiment 5, with N-heterocyclic carbine Palladous chloride dimer ([(SIPr) PdCl
2]
2) replace N-heterocyclic carbine Palladous chloride dimer ([(IPr) PdCl
2]
2).Product is yellow solid, yield 86%.Its physical constant characterizes with embodiment 2.
Embodiment 7: N-heterocyclic carbine pyridine-2,6-dicarboxylic acid palladium (IPr) Pd (Py-2,6-dicaboxylate)
Synthetic method, with embodiment 5, replaces 2-pyridine carboxylic acid with 2,6-dinicotinic acid.Product is yellow solid, yield 85%.Its physical constant characterizes with embodiment 3.
Embodiment 8: N-heterocyclic carbine pyridine-2,6-dicarboxylic acid palladium (SIPr) Pd (Py-2,6-dicaboxylate)
Synthetic method, with embodiment 6, replaces 2-pyridine carboxylic acid with 2,6-dinicotinic acid.Product is yellow solid, yield 83%.Its physical constant characterizes with embodiment 4.
Embodiment 9: the halogenated aryl hydrocarbon of palladium chtalyst and the C-N cross-coupling reaction of organic amine
Under argon atmosphere, N-heterocyclic carbine pyridine-2 is added in the Schlenk bottle of drying, 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 Isosorbide-5-Nitrae-dioxane.By reaction soln stirring reaction 10-120 minute at 100 DEG C.Product is by purification by silica gel column chromatography, and petrol ether/ethyl acetate (20: 1) is as eluent, and yield results is in table 1.Table 1 is the halogenated aryl hydrocarbon of palladium chtalyst and the C-N cross-coupling reaction result of 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 (5)
1. one kind contains the N-heterocyclic carbine palladium mixture of the two formate parts of pyridine-2,6-, it is characterized in that having following structural formula:
Wherein: n=0;
r
3=R
4=H, R
5for H.
2. the preparation method of a N-heterocyclic carbine palladium mixture according to claim 1, it is characterized in that the step comprised: with corresponding imidazoles or imidazoline salt, Palladous chloride and 2, dipicolimic acid 2 is starting raw material, under salt of wormwood or cesium carbonate effect, at 90 ~ 100 DEG C of temperature, react 12-24 hour in organic solvent, generate the N-heterocyclic carbine palladium mixture containing the two formate part of pyridine-2,6-; Imidazoles or imidazoline salt, palladium chloride and 2, the mol ratio of dipicolimic acid 2 is 1.2: 1: 1.1; Organic solvent is at least one in Isosorbide-5-Nitrae-dioxane, glycol dimethyl ether, DMF:
X is chlorine, hexafluoro-phosphate radical or tetrafluoroborate.
3. the preparation method of a N-heterocyclic carbine palladium mixture according to claim 1, it is characterized in that the step comprised: with corresponding N-heterocyclic carbine Palladous chloride dimer and 2, dipicolimic acid 2 is starting raw material, under salt of wormwood or cesium carbonate effect, at 90 ~ 100 DEG C of temperature, react 10-12 hour in organic solvent, generate the N-heterocyclic carbine palladium mixture containing the two formate part of pyridine-2,6-; N-heterocyclic carbine palladium chloride dimer and 2, the mol ratio of dipicolimic acid 2 is 1: 2.0 ~ 3.0; Organic solvent is selected from one or more in Isosorbide-5-Nitrae-dioxane, glycol dimethyl ether, DMF::
4. the application of N-heterocyclic carbine palladium mixture according to claim 1, is characterized in that this compound as catalyzer in the presence of a base for the C-N cross-coupling reaction of halogenated aryl hydrocarbon and organic amine.
5. the application of N-heterocyclic carbine palladium mixture according to claim 4, is characterized in that comprising following step:
In solvent under argon gas or nitrogen atmosphere and N-heterocyclic carbine palladium complex catalyst exist, halogenated aryl hydrocarbon and organic amine stirring reaction 10 minutes ~ 120 minutes, product passes through purification by silica gel column chromatography; Petrol ether/ethyl acetate, 20: 1, volume ratio, 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 DEG C; Solvent is one or more in Isosorbide-5-Nitrae-dioxane, glycol dimethyl ether or 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
10phenyl, C that alkyl replaces
1~ C
10phenyl, naphthyl, furyl, thienyl, pyridyl that alkoxyl group replaces; 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, cycloalkyl, benzyl, phenyl, C
1~ C
10phenyl, C that alkyl replaces
1~ C
10phenyl, naphthyl, furyl, thienyl, pyridyl that alkoxyl group replaces; R
11, R
12identical or different.
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| CN103242371B (en) * | 2013-05-29 | 2016-05-18 | 洛阳师范学院 | Biaryl pyridine ring palladium N-heterocyclic carbine compound and its production and use |
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