CN104098607B - Containing single phosphine list N-heterocyclic carbine nickel (II) title complex and the application thereof of tricyclohexyl phosphine - Google Patents
Containing single phosphine list N-heterocyclic carbine nickel (II) title complex and the application thereof of tricyclohexyl phosphine Download PDFInfo
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Abstract
The invention discloses a kind of single phosphine list N-heterocyclic carbine nickel (II) title complex containing tricyclohexyl phosphine and application thereof, the molecular formula of described single phosphine list N-heterocyclic carbine nickel (II) title complex containing tricyclohexyl phosphine is (PCy
3) Ni [(RNCHCHNR) C] X
2, in formula, PCy
3for tricyclohexyl phosphine; R is the tertiary butyl, 2,6-diisopropyl phenyls or mesitylene base; X is chlorine or bromine.In the present invention containing single phosphine list N-heterocyclic carbine nickel (II) title complex of tricyclohexyl phosphine, prepare simple to operation, product easily purified, yield is high, and in atmosphere also Absorbable organic halogens exist.This kind of single phosphine list N-heterocyclic carbine nickel (II) title complex can efficient catalytic virtue methyl ether and the cross-coupling reaction of aryl grignard reagent in a mild condition.
Description
Technical field
The present invention relates to a kind of N-heterocyclic carbine nickel (II) title complex, be specifically related to a kind of containing the application in single phosphine list N-heterocyclic carbine nickel (II) title complex of tricyclohexyl phosphine and the cross-coupling reaction between aryl grignard reagent and fragrant methyl ether thereof.
Background technology
Aryl-linking compound, is extensively present in natural product and drug molecule, is also industrial important fine chemicals, pharmaceutical intermediate, white dyes and agricultural chemicals.In recent years, intensification chemical industry Sustainable development is familiar with along with people and the enhancing of environmental consciousness, cross-coupling reaction between phenol derivatives that is transition metal-catalyzed, that realized by the activation of carbon-oxygen bond and aryl grignard reagent receives increasing concern, is just becoming an important method of constructing biaryl structure.Compared with traditional halogenated aryl hydrocarbon substrate, the great advantage of phenol derivatives very easily obtains, and they extensively exist at nature and on aromatic ring, introduce other substituting group easily via the synthesis of other aromatic compound or easily via the method such as electrophilic substitution reaction of phenol derivatives.Therefore, using phenol derivatives as electrophilic reagent, replace halogenated aryl hydrocarbon and aryl grignard reagent to carry out cross-coupling reaction preparing aryl-linking compound and become a kind of development trend.At present, compared with other phenol derivatives, be that the research report of electrophilic reagent is less with aryl oxide.
In cross-coupling reaction between aryl grignard reagent and aryl oxide, catalyzer is the key of reaction.Compared with palladium series catalyst, nickel catalyst not only has cheap and easy to get, the easy feature such as removing in process after the reaction, and due to nickle atom radius is less, nucleophilicity is of value to more by force and more carbon-oxygen bond priming reaction.Therefore, design and synthesis nickel catalyst, by carbon-oxygen bond activation prepare aryl-linking compound becoming in recent years cross-coupling reaction research in a focus.
2004, Dankwardt seminar finds that two (tricyclohexyl phosphine) nickel (II) title complex of a class can the cross-coupling reaction of catalysis aryl oxide and aryl grignard reagent effectively, this reaction optimal conditions is: the mol ratio of 2-naphthol methyl ether and phenyl-magnesium-bromide is 1: 3, catalyst levels is 2.5mol%, add the tricyclohexyl phosphine of 5mol%, 15 hours are reacted in the mixed solvent of tert amyl methyl ether(TAME) and ether, temperature is 23 DEG C, the yield of cross-coupling products can reach 89%(see Dankwardt, J.W.Angew.Chem.Int.Ed., 2004,43,2428); But this reaction system also exists some shortcomings, the amount ratio as required Grignard reagent is comparatively large, need are extra adds Phosphine ligands etc.
2011; the Phosphine ligands containing heterocyclic skeleton that Wang Zhongxia seminar design and synthesis one class is novel; and synthesized corresponding two phosphine nickel (II) title complex; find that they can catalysis virtue methyl ether and the cross-coupling reaction of aryl grignard reagent; this reaction optimal conditions is: the mol ratio of 2-naphthol methyl ether and p-methylphenyl magnesium bromide is 1: 1.5; catalyst levels is 2.5mol%; react 24 hours in tetrahydrofuran solvent; temperature is 25 DEG C; the yield of cross-coupling products can reach 92% (see Xie, L.-G.; Wang, Z.-X.Chem.Eur.J., 2011,17,4972.); But this reaction system also exists some problems, as the complex structure of Phosphine ligands used, preparation process are loaded down with trivial details, partial intersection linked reaction just can need be carried out at 120 DEG C.
The complex-catalyzed above-mentioned reaction of nickel (II) is electrophilic reagent and the cross-coupling reaction of nucleophilic reagent under nickel (II) is complex-catalyzed, comprises oxidation addition, turns metallization and reduction elimination three steps; According to such reaction mechanism, single phosphine list N-heterocyclic carbine nickel (II) title complex of the nitrogen heterocycle carbine ligand containing the easily reversible Phosphine ligands that dissociates and strong metal coordination should be advantageously in this kind of cross-coupling reaction of catalysis.
Within 2006, Matsubara seminar is passing through two phosphine nickel (II) title complex (PPh
3)
2niX
2single phosphine N-heterocyclic carbine nickel (II) title complex (PPh of first case containing triphenylphosphine has been separated to very by accident during (N-heterocyclic carbine) nickel (II) title complex two with the Reactive Synthesis of N-heterocyclic carbine
3) Ni [(RNCHCHNR) C] X
2(PPh
3for triphenylphosphine, R is 2,6-diisopropyl phenyl, and X is chlorine or bromine) (see: Matsubara, K.; Ueno, K.; Shibata, Y.Organometallics, 2006,25,3422), but when they adopt other nitrogen heterocycle carbine ligand, attempt nickel (II) title complex being expanded this kind of mixed matching by this reaction time there is no successfully, and two (N-heterocyclic carbine) nickel (II) title complex can only be obtained.
Therefore, so far yet there are no the report of single phosphine list N-heterocyclic carbine nickel (II) title complex containing other Phosphine ligands or other nitrogen heterocycle carbine ligand, more not about the report of such mixed matching nickel (II) title complex catalytic applications in the cross-coupling reaction of aryl oxide and aryl grignard reagent.
Summary of the invention
The object of this invention is to provide a kind of single phosphine list N-heterocyclic carbine nickel (II) title complex containing tricyclohexyl phosphine, it can the cross-coupling reaction of the virtue methyl ether of catalysis efficiently and aryl grignard reagent.
To achieve the above object of the invention, the technical solution used in the present invention is: a kind of single phosphine list N-heterocyclic carbine nickel (II) title complex containing tricyclohexyl phosphine, is expressed by the following chemical structure formula:
，
In formula, Cy is cyclohexyl; R is the tertiary butyl, 2,6-diisopropyl phenyls or mesitylene base; X is chlorine or bromine.
The preparation method of above-mentioned single phosphine list N-heterocyclic carbine nickel (II) title complex containing tricyclohexyl phosphine comprises the following steps:
[1] under anhydrous and oxygen-free condition, in inert gas atmosphere, single phosphine mono-quaternaries nickel (II) title complex and N-heterocyclic carbine are dissolved in solvent, react 1 ~ 4 hour at 0 ~ 45 DEG C; Then add tricyclohexyl phosphine, then react 1 ~ 4 hour at 0 ~ 45 DEG C;
The molecular formula of described single phosphine mono-quaternaries nickel (II) title complex is: [N (C
2h
5)
4] [Ni (PPh
3) X
3], wherein PPh
3for triphenylphosphine, X is chlorine or bromine; The general structure of described N-heterocyclic carbine is: (RNCHCHNR) C, and wherein R is selected from the tertiary butyl, 2,6-diisopropyl phenyls or mesitylene base;
[2] except desolventizing, residuum with after saturated alkane washing, then through toluene extraction, obtains solution; Solution obtains solid through recrystallization, is single phosphine list N-heterocyclic carbine nickel (II) title complex containing tricyclohexyl phosphine.
In technique scheme, in step [1], described rare gas element is nitrogen or argon gas, and described solvent is not containing the solvent of reactive hydrogen, such as tetrahydrofuran (THF) or methylene dichloride.Solvent is in order to solubilizing reaction thing; Be preferably tetrahydrofuran (THF).
In technique scheme, the mol ratio of single phosphine mono-quaternaries nickel (II) title complex, N-heterocyclic carbine, tricyclohexyl phosphine is (1 ~ 1.2): 1: 1; Be preferably 1: 1: 1.
In preferred technical scheme, in step [1], under anhydrous and oxygen-free condition, in inert gas atmosphere, single phosphine mono-quaternaries nickel (II) title complex and N-heterocyclic carbine are dissolved in solvent, react 2 hours at 25 DEG C; Then add tricyclohexyl phosphine, then react 2 hours at 25 DEG C.
In technique scheme, in step [2], described saturated alkane is hexane or sherwood oil; Add normal hexane in the solution and carry out recrystallization.
Application in the cross-coupling reaction that the present invention asks to protect above-mentioned single phosphine list N-heterocyclic carbine nickel (II) title complex containing tricyclohexyl phosphine to carry out at catalysis aryl grignard reagent and fragrant methyl ether as single-component catalyst simultaneously.
Above-mentioned single phosphine list N-heterocyclic carbine nickel (II) title complex containing tricyclohexyl phosphine carries out the method for cross-coupling reaction as single component catalyst catalysis aryl grignard reagent and fragrant methyl ether, comprise the following steps: under anhydrous and oxygen-free condition, in inert gas atmosphere, under ice-water bath condition, catalyzer, tetrahydrofuran (THF), aryl grignard reagent and fragrant methyl ether are mixed, in 25 ~ 55 DEG C of stirring reactions 10 hours, use deionized water termination reaction; Reactant through extraction, then through chromatography column separating-purifying, obtains product, i.e. aryl-linking compound.
In preferred technical scheme, first catalyzer, tetrahydrofuran (THF) and fragrant methyl ether are mixed, more slowly drip aryl grignard reagent.
In technique scheme, described rare gas element is nitrogen or argon gas.
In technique scheme, fragrant methyl ether comprises 1-naphthol methyl ether, 2-naphthol methyl ether, methyl-phenoxide and they are containing substituent derivative etc., and aryl grignard reagent comprises phenyl-magnesium-bromide, phenyl-magnesium-chloride and they are containing substituent derivative etc.
In technique scheme, the mol ratio of fragrant methyl ether and aryl grignard reagent is 1: (1 ~ 2); The consumption of catalyzer is 1 ~ 5mol% of fragrant methyl ether.
In preferred technical scheme, when substrate is naphthol methyl ether, the mol ratio of aryl grignard reagent and naphthol methyl ether is 1.5: 1, and the consumption of catalyzer is the 1mol% of naphthol methyl ether, and temperature of reaction is 25 DEG C; When substrate is methyl-phenoxide, the mol ratio of aryl grignard reagent and methyl-phenoxide is 1.5: 1, and the consumption of catalyzer is the 5mol% of methyl-phenoxide, and temperature is 55 DEG C.
In the present invention, except desolventizing, termination reaction, extraction, column chromatography for separation are purified and belonged to prior art; Extraction into ethyl acetate reactant can be selected, then be that developping agent carries out column chromatography for separation purification with sherwood oil.
The present invention with single phosphine mono-quaternaries nickel (II) title complex containing triphenylphosphine cheap and easy to get with N-heterocyclic carbine for raw material, prepared single phosphine list N-heterocyclic carbine nickel (II) title complex containing tricyclohexyl phosphine first.This title complex is by the effect with aryl grignard reagent, lower valency nickel active intermediate by tricyclohexyl phosphine and nitrogen heterocycle carbine ligand jointly stabilizing can be become by in-situ transesterification, thus described single phosphine list N-heterocyclic carbine nickel (II) title complex containing tricyclohexyl phosphine is changed at reaction system situ can the catalyzer of cross-coupling reaction of efficient catalytic virtue methyl ether and aryl grignard reagent.
Because technique scheme is used, the present invention compared with prior art has following advantages:
1. thricyclohexyl Phosphine ligands is introduced in this kind of mixed matching nickel (II) title complex by single phosphine list N-heterocyclic carbine nickel (II) title complex disclosed by the invention first, substituting group simultaneously in Cabbeen ring on nitrogen-atoms also can variously be selected, and is the effective catalyst that a class is new.
2. the present invention is single phosphine list N-heterocyclic carbine nickel (II) title complex that nickel source has synthesized containing tricyclohexyl phosphine with single phosphine mono-quaternaries nickel (II) title complex containing triphenylphosphine cheap and easy to get, react simple to operation, product is easily purified, yield is high, and also Absorbable organic halogens existence in atmosphere.
3. single phosphine list N-heterocyclic carbine nickel (II) title complex containing tricyclohexyl phosphine disclosed by the invention has high catalytic activity to the cross-coupling reaction between aryl grignard reagent and fragrant methyl ether, when its consumption is 1% of fragrant methyl ether molar weight, reaction yield is up to 93%, equal or higher with the most high catalytic activity of the catalyst system reported at present.
Embodiment
Below in conjunction with embodiment, the invention will be further described:
Embodiment one: (PCy
3) Ni [(RNCHCHNR) C] X
2; R is the tertiary butyl, and X is Cl
Under anhydrous and oxygen-free condition, in nitrogen atmosphere, [(RNCHCHNR) C] (0.18 gram, 1.0 mmoles, R is the tertiary butyl) is joined [N (C
2h
5)
4] [Ni (PPh
3) Cl
3] (0.56 gram, 1.0 mmoles) tetrahydrofuran solution in, at 25 DEG C stir 2 hours.Then by PCy
3(0.28 gram, 1.0 mmoles) join in reaction system, and stir 2 hours at 25 DEG C, pump solvent, hexanes wash, with toluene extraction residuum, a clear liquid is obtained after centrifugal, in clear liquid, add normal hexane recrystallization, the crystal of separating out purple at 0 DEG C is single phosphine list N-heterocyclic carbine nickel (II) title complex containing tricyclohexyl phosphine, productive rate 84%.
Carry out ultimate analysis to product, result is:
Theoretical value: C59.00%, H9.05%, N4.75%; Measured value: C59.11%, H9.11%, N4.91%.
Above-mentioned title complex is dissolved in C
6d
6in (about 0.4 milliliter), tube sealing, under room temperature on UnityInova-400 type NMR instrument measure characterize: 6.45 (s, 2H, C
h=c
h), 2.48-2.45 (m, 21H, P (C
6 h 11)
3+ C (C
h 3)
3), 2.21-2.18 (m, 6H, P (C
6 h 11)
3), 2.00-1.83 (m, 12H, P (C
6 h 11)
3), 1.73-1.70 (m, 3H, P (C
6 h 11)
3), 1.38-1.25 (m, 9H, P (C
6 h 11)
3),
13cNMR (
d, 100MHz, C
6d
6): 155.69 (d,
j pC=108.7Hz), 119.77 (d,
j pC=3.8Hz), 58.66,32.55,31.29 (d,
j pC=16.8Hz), 29.39,27.78 (d,
j pC=9.9Hz), 26.59.
Embodiment two: (PCy
3) Ni [(RNCHCHNR) C] X
2; R is the tertiary butyl, and X is Br
Under anhydrous and oxygen-free condition, in argon gas atmosphere, [(RNCHCHNR) C] (0.18 gram, 1.0 mmoles, R is the tertiary butyl) is joined [N (C
2h
5)
4] [Ni (PPh
3) Br
3] (0.83 gram, 1.2 mmoles) tetrahydrofuran solution in, at 0 DEG C stir 3 hours, then by PCy
3(0.28 gram, 1.0 mmoles) join in reaction system, and stir 1 hour at 25 DEG C, pump solvent, sherwood oil (60 DEG C-90 DEG C) washs, with toluene extraction residuum, a clear liquid is obtained after centrifugal, in clear liquid, add normal hexane recrystallization, the crystal of separating out purple at 0 DEG C is single phosphine list N-heterocyclic carbine nickel (II) title complex containing tricyclohexyl phosphine, productive rate 70%.
Carry out ultimate analysis to product, result is as follows:
Theoretical value: C51.28%, H7.87%, N4.12%; Measured value: C51.19%, H7.79%, N4.18%.
Above-mentioned title complex is dissolved in C
6d
6in (about 0.4 milliliter), tube sealing, under room temperature on UnityInova-400 type NMR instrument measure characterize:
1hNMR (
d, 400MHz, C
6d
6): 6.47 (s, 2H, C
h=c
h), 2.50-2.47 (m, 21H, P (C
6 h 11)
3+ C (C
h 3)
3), 2.22-2.19 (m, 6H, P (C
6 h 11)
3), 2.00-1.83 (m, 12H, P (C
6 h 11)
3), 1.73-1.70 (m, 3H, P (C
6 h 11)
3), 1.38-1.25 (m, 9H, P (C
6 h 11)
3),
13cNMR (
d, 100MHz, C
6d
6): 156.69 (d,
j pC=110.5Hz), 119.87 (d,
j pC=3.6Hz), 58.88,32.81,31.39 (d,
j pC=17.3Hz), 29.45,27.86 (d,
j pC=9.7Hz), 26.88.
Embodiment three: (PCy
3) Ni [(RNCHCHNR) C] X
2; R is 2,6-diisopropyl phenyl, and X is Br
Under anhydrous and oxygen-free condition, in nitrogen atmosphere, [(RNCHCHNR) C] (0.39 gram, 1.0 mmoles, R is 2,6-diisopropyl phenyl) is joined [N (C
2h
5)
4] [Ni (PPh
3) Br
3] (0.83 gram, 1.2 mmoles) tetrahydrofuran solution in, at 45 DEG C stir 1 hour, then by PCy
3(0.28 gram, 1.0 mmoles) join in reaction system, and stir 4 hours at 0 DEG C, pump solvent, sherwood oil (30 DEG C-60 DEG C) washs, with toluene extraction residuum, a clear liquid is obtained after centrifugal, in clear liquid, add normal hexane recrystallization, the crystal of separating out purple at 5 DEG C is single phosphine list N-heterocyclic carbine nickel (II) title complex containing tricyclohexyl phosphine, productive rate 79%.
Carry out ultimate analysis to product, result is as follows:
Theoretical value: C60.90%, H7.84%, N3.16%; Measured value: C60.88%, H7.81%, N3.22%.
Above-mentioned title complex is dissolved in C
6d
6in (about 0.4 milliliter), tube sealing, under room temperature on UnityInova-400 type NMR instrument measure characterize:
1hNMR (
d, 400MHz, C
6d
6): 7.41-7.34 (m,
6h,C
6 h 3), 6.61 (s, 2H, C
h=c
h), 3.53-3.47 (m, 4H, C
h(CH
3)
2), 2.16-2.11 (m, 3H, P (C
6 h 11)
3), 1.88-1.85 (m, 6H, P (C
6 h 11)
3), 1.65-1.60 (m, 27H, CH (C
h 3)
2+ P (C
6 h 11)
3), 1.23-1.08 (m, 9H, P (C
6 h 11)
3), 1.04 (d,
j=6.8Hz, 12H, CH (C
h 3)
2),
13cNMR (
d, 100MHz, C
6d
6): 170.25 (d,
j pC=118.4Hz), 147.58,136.31,130.07,124.75 (d,
j pC=3.5Hz), 123.80,32.65 (d,
j pC=18.1Hz), 29.86,29.04,27.82 (d,
j pC=9.9Hz), 26.67,26.56,22.94.
Embodiment four: (PCy
3) Ni [(RNCHCHNR) C] X
2; R is mesitylene base, and X is Br
Under anhydrous and oxygen-free condition, in argon gas atmosphere, [(RNCHCHNR) C] (0.30 gram, 1.0 mmoles, R is mesitylene base) is joined [N (C
2h
5)
4] [Ni (PPh
3) Br
3] (0.69 gram, 1.0 mmoles) dichloromethane solution in, at 0 DEG C stir 4 hours, then by PCy
3(0.28 gram, 1.0 mmoles) join in reaction system, and stir 3 hours at 45 DEG C, pump solvent, hexanes wash, with toluene extraction residuum, a clear liquid is obtained after centrifugal, in clear liquid, add normal hexane recrystallization, the crystal of separating out purple at 0 DEG C is single phosphine list N-heterocyclic carbine nickel (II) title complex containing tricyclohexyl phosphine, productive rate 73%.
Carry out ultimate analysis to product, result is as follows:
Theoretical value: C58.31%, H7.15%, N3.49%; Measured value: C58.36%, H7.18%, N3.46%.
Above-mentioned title complex is dissolved in C
6d
6in (about 0.4 milliliter), tube sealing, under room temperature on UnityInova-400 type NMR instrument measure characterize:
1hNMR (
d, 400MHz, C
6d
6): 6.96-6.94 (s, 4H, C
6 h 2)., 6.27 (s, 2H, C
h=c
h), 2.54 (s, 12H, C
h 3), 2.22-2.18 (m, 9H, C
h 3+ P (C
6 h 11)
3) 1.91-1.87 (m, 6H, P (C
6 h 11)
3), 1.68-1.64 (m, 15H, P (C
6 h 11)
3), 1.33-1.28 (m, 9H, P (C
6 h 11)
3),
13cNMR (
d, 100MHz, C
6d
6): 174.88 (d,
j pC=114.8Hz), 138.97,137.68,136.78,129.44,122.89,31.66 (d,
j pC=17.5Hz), 29.78,27.94 (d,
j pC=9.9Hz), 26.44,23.35,21.53.
Embodiment five: (PCy
3) [(RNCHCHNR) C] NiX
2; (R is the tertiary butyl, and X the is Br) phenyl-magnesium-bromide of catalysis and the cross-coupling reaction of 2-naphthol methyl ether
In the reaction flask through dehydration and deoxidation process, under argon shield, add 2-naphthol methyl ether 158.07 milligrams (1.0 mmole) successively, catalyzer 6.79 milligrams (0.01 mmole) and tetrahydrofuran (THF) 0.5 milliliter.Tetrahydrofuran solution 1.5 milliliters of (1.00 mmoles × milliliters of phenyl-magnesium-bromide are slowly dripped at 0 DEG C
-1), stir 5 minutes.Stirring reaction 10 hours after rising to 25 DEG C, use deionized water termination reaction, reaction solution is extracted with ethyl acetate, and chromatography column is purified (taking sherwood oil as developping agent), obtains product 2-phenylnaphthalene, productive rate 90%.
Coupled product is dissolved in CDCl
3in (about 0.4 milliliter), tube sealing, measures under room temperature and characterizes: 8.05 (s, 1H) on UnityInova-400 type NMR instrument, 7.94-7.87 (m, 3H), 7.78-7.73 (m, 3H), 7.52-7.48 (m, 4H), 7.41-7.38 (m, 1H).
Embodiment six: (PCy
3) [(RNCHCHNR) C] NiX
2; (R is the tertiary butyl, and X the is Cl) phenyl-magnesium-chloride of catalysis and the cross-coupling reaction of 2-naphthol methyl ether
In the reaction flask through dehydration and deoxidation process, under argon shield, add 2-naphthol methyl ether 158.07 milligrams (1.0 mmole) successively, catalyzer 5.90 milligrams (0.01 mmole) and tetrahydrofuran (THF) 0.5 milliliter.Tetrahydrofuran solution 1.5 milliliters of (1.00 mmoles × milliliters of phenyl-magnesium-chloride are slowly dripped at 0 DEG C
-1), stir 5 minutes.Stirring reaction 10 hours after rising to 25 DEG C, use deionized water termination reaction, reaction solution is extracted with ethyl acetate, and chromatography column is purified (taking sherwood oil as developping agent), obtains product 2-phenylnaphthalene, productive rate 86%.
Coupled product is dissolved in CDCl
3in (about 0.4 milliliter), tube sealing, measures under room temperature and characterizes: 8.05 (s, 1H) on UnityInova-400 type NMR instrument, 7.94-7.87 (m, 3H), 7.78-7.73 (m, 3H), 7.52-7.48 (m, 4H), 7.41-7.38 (m, 1H).
Embodiment seven: (PCy
3) [(RNCHCHNR) C] NiX
2; (R is the tertiary butyl, and X is Br) the 4-methylphenyl magnesium bromide of catalysis and the cross-coupling reaction of 2-naphthol methyl ether
In the reaction flask through dehydration and deoxidation process, under argon shield, add 2-naphthol methyl ether 158.07 milligrams (1.0 mmole) successively, catalyzer 6.79 milligrams (0.01 mmole) and tetrahydrofuran (THF) 0.5 milliliter.Tetrahydrofuran solution 1.5 milliliters of (1.00 mmoles × milliliters of 4-methylphenyl magnesium bromide are slowly dripped at 0 DEG C
-1), stir 5 minutes.Stirring reaction 10 hours after rising to 25 DEG C, use deionized water termination reaction, reaction solution is extracted with ethyl acetate, and chromatography column is purified (taking sherwood oil as developping agent), obtains product 2-(4-aminomethyl phenyl) naphthalene, productive rate 93%.
Coupled product is dissolved in CDCl
3in (about 0.4 milliliter), tube sealing, under room temperature on UnityInova-400 type NMR instrument measure characterize: 8.05 (s, 1H), 7.94-7.87 (m, 3H), 7.78-7.76 (m, 1H), 7.67-7.65 (m, 2H), 7.54-7.48 (m, 2H), (7.33 d, J=7.9Hz, 2H), 2.45 (s, 3H).
Embodiment eight: Ni (PCy
3) [(RNCHCHNR) C] NiX
2; (R is 2,6-diisopropyl phenyl, and X is Br) the 4-methoxyphenyl-magnesium bromide of catalysis and the cross-coupling reaction of 2-naphthol methyl ether
In the reaction flask through dehydration and deoxidation process, under argon shield, add 2-naphthol methyl ether 158.07 milligrams (1.0 mmole) successively, catalyzer 17.7 milligrams (0.02 mmole) and tetrahydrofuran (THF) 0.5 milliliter.Tetrahydrofuran solution 1.5 milliliters of (1.00 mmoles × milliliters of 4-methoxyphenyl-magnesium bromide are slowly dripped at 0 DEG C
-1), stir 5 minutes.Stirring reaction 10 hours after rising to 25 DEG C, use deionized water termination reaction, reaction solution is extracted with ethyl acetate, and chromatography column is purified (taking sherwood oil as developping agent), obtains product 2-(4-p-methoxy-phenyl) naphthalene, productive rate 95%.
Coupled product is dissolved in CDCl
3in (about 0.4 milliliter), tube sealing, under room temperature on UnityInova-400 type NMR instrument measure characterize: 8.01 (s, 1H), 7.92-7.86 (m, 3H), 7.75-7.67 (m, 3H), 7.53-7.46 (m, 2H), 7.06-7.03 (m, 2H), 3.89 (s, 3H).
Embodiment nine: (PCy
3) [(RNCHCHNR) C] NiX
2; (R is the tertiary butyl, and X is Br) the 4-diformazan aminophenyl magnesium bromide of catalysis and the cross-coupling reaction of 2-naphthol methyl ether
In the reaction flask through dehydration and deoxidation process, under argon shield, add 2-naphthol methyl ether 158.07 milligrams (1.0 mmole) successively, catalyzer 6.79 milligrams (0.01 mmole) and tetrahydrofuran (THF) 0.5 milliliter.Tetrahydrofuran solution 1.5 milliliters of (1.33 mmoles × milliliters of 4-diformazan aminophenyl magnesium bromide are slowly dripped at 0 DEG C
-1), stir 5 minutes.Stirring reaction 10 hours after rising to 50 DEG C, use deionized water termination reaction, reaction solution is extracted with ethyl acetate, and chromatography column is purified (taking sherwood oil as developping agent), obtains product 2-(4-dimethylamino phenyl) naphthalene, productive rate 93%.
Coupled product is dissolved in CDCl
3in (about 0.4 milliliter), tube sealing, under room temperature on UnityInova-400 type NMR instrument measure characterize: 8.02 (s, 1H), 7.91-7.85 (m, 3H), 7.79-7.76 (m, 1H), 7.69-7.67 (m, 2H), 7.52-7.44 (m, 2H), (6.88 d, J=8.8Hz, 2H), 3.04 (s, 6H).
Embodiment ten: (PCy
3) [(RNCHCHNR) C] NiX
2; (R is mesitylene base, and X is Br) the 2-methylphenyl magnesium bromide of catalysis and the cross-coupling reaction of 2-naphthol methyl ether
In the reaction flask through dehydration and deoxidation process, under argon shield, add 2-naphthol methyl ether 158.07 milligrams (1.0 mmole) successively, catalyzer 8.02 milligrams (0.01 mmole) and tetrahydrofuran (THF) 0.8 milliliter.Tetrahydrofuran solution 1.2 milliliters of (1.00 mmoles × milliliters of 2-methylphenyl magnesium bromide are slowly dripped at 0 DEG C
-1), stir 5 minutes.Stirring reaction 10 hours after rising to 55 DEG C, use deionized water termination reaction, reaction solution is extracted with ethyl acetate, and chromatography column is purified (taking sherwood oil as developping agent), obtains product 2-(2-aminomethyl phenyl) naphthalene, productive rate 88%.
Coupled product is dissolved in CDCl
3in (about 0.4 milliliter), tube sealing, measures under room temperature and characterizes: 7.97-7.93 (m, 3H) on UnityInova-400 type NMR instrument, 7.87-7.86 (m, 1H), 7.60-7.55 (m, 3H), 7.43-7.34 (m, 4H), 2.41 (s, 3H).
Embodiment 11: (PCy
3) [(RNCHCHNR) C] NiX
2; (R is the tertiary butyl, and X is Br) the 4-methoxyphenyl-magnesium bromide of catalysis and the cross-coupling reaction of 1-naphthol methyl ether
In the reaction flask through dehydration and deoxidation process, under argon shield, add 1-naphthol methyl ether 145.13 microlitre (1.0 mmole) successively, catalyzer 6.79 milligrams (0.01 mmole) and tetrahydrofuran (THF) 1.0 milliliters.Tetrahydrofuran solution 1.0 milliliters of (1.00 mmoles × milliliters of 4-methoxyphenyl-magnesium bromide are slowly dripped at 0 DEG C
-1), stir 5 minutes.Rise to 25 DEG C of stirring reactions 10 hours, use deionized water termination reaction, reaction solution is extracted with ethyl acetate, and chromatography column is purified (taking sherwood oil as developping agent), obtains product 1-(4-p-methoxy-phenyl) naphthalene, productive rate 87%.
Coupled product is dissolved in CDCl
3in (about 0.4 milliliter), tube sealing, under room temperature on UnityInova-400 type NMR instrument measure characterize: 8.00 (d, J=8.4Hz, 1H), 7.95 (d, J=8.0Hz, 1H), 7.89 (d, J=8.2Hz, 1H), 7.58 7.46 (m, 6H), 7.09 (d, J=8.5Hz, 2H), 3.93 (s, 3H).
Embodiment 12: (PCy
3) [(RNCHCHNR) C] NiX
2; The 4-methylphenyl magnesium bromide of (R is the tertiary butyl, and X is Br) catalysis and 6-(2-aminomethyl phenyl) cross-coupling reaction of-2-naphthol methyl ether
In the reaction flask through dehydration and deoxidation process, under argon shield, add 6-(2-aminomethyl phenyl successively)-2-naphthol methyl ether 248.32 milligrams (1.0 mmole), catalyzer 6.79 milligrams (0.01 mmole) and tetrahydrofuran (THF) 0.5 milliliter.Tetrahydrofuran solution 1.5 milliliters of (1.00 mmoles × milliliters of 4-methylphenyl magnesium bromide are slowly dripped at 0 DEG C
-1), stir 5 minutes.Rise to 25 DEG C of stirring reactions 10 hours, use deionized water termination reaction, reaction solution is extracted with ethyl acetate, and chromatography column is purified (taking sherwood oil as developping agent), obtains product 2-(4-aminomethyl phenyl)-6-(2-aminomethyl phenyl) naphthalene, productive rate 94%.
Coupled product is dissolved in CDCl
3in (about 0.4 milliliter), tube sealing, under room temperature on UnityInova-400 type NMR instrument measure characterize: 8.17 (s, 1H), 8.02-8.00 (m, 2H), 7.90-7.86 (m, 2H), 7.75 (d, J=8.0Hz, 2H), 7.61-7.59 (m, 1H), 7.47-7.39 (m, 6H), 2.53 (s, 3H), 2.44 (s, 3H).
Embodiment 13: (PCy
3) [(RNCHCHNR) C] NiX
2; (R is 2,6-diisopropyl phenyl, and X is Br) the 4-methylphenyl magnesium bromide of catalysis and the cross-coupling reaction of methyl-phenoxide
In the reaction flask through dehydration and deoxidation process, under argon shield, add methyl-phenoxide 108.13 microlitre (1.0 mmole) successively, catalyzer 44.30 milligrams (0.05 mmole) and tetrahydrofuran (THF) 0.5 milliliter.Tetrahydrofuran solution 1.5 milliliters of (1.00 mmoles × milliliters of 4-methylphenyl magnesium bromide are slowly dripped at 0 DEG C
-1), stir 5 minutes.Stirring reaction 10 hours after rising to 55 DEG C, use deionized water termination reaction, reaction solution is extracted with ethyl acetate, and chromatography column is purified (taking sherwood oil as developping agent), obtains product 4-methyl diphenyl, productive rate 65%.
Coupled product is dissolved in CDCl
3in (about 0.4 milliliter), tube sealing, under room temperature on UnityInova-400 type NMR instrument measure characterize: 7.66 (d, J=8.0Hz, 2H), 7.58 (d, J=7.7Hz, 2H), 7.50 (t, J=7.5Hz, 2H), 7.40 (t, J=7.3Hz, 1H), 7.33 (d, J=7.7Hz, 2H), 2.47 (s, 3H).
Claims (9)
1., containing the preparation method of single phosphine list N-heterocyclic carbine nickel (II) title complex of tricyclohexyl phosphine, it is characterized in that, comprise the following steps:
[1] under anhydrous and oxygen-free condition, in inert gas atmosphere, single phosphine mono-quaternaries nickel (II) title complex and N-heterocyclic carbine are dissolved in solvent, react 1 ~ 4 hour at 0 ~ 45 DEG C; Then add tricyclohexyl phosphine, then react 1 ~ 4 hour at 0 ~ 45 DEG C;
The molecular formula of described single phosphine mono-quaternaries nickel (II) title complex is: [N (C
2h
5)
4] [Ni (PPh
3) X
3], wherein PPh
3for triphenylphosphine, X is chlorine or bromine; The general structure of described N-heterocyclic carbine is: (RNCHCHNR) C, and wherein R is selected from the tertiary butyl, 2,6-diisopropyl phenyls or mesitylene base;
[2] reaction terminate after except desolventizing, after residuum hexane or petroleum ether, then through toluene extraction, obtain solution; Solution obtains solid through recrystallization, is single phosphine list N-heterocyclic carbine nickel (II) title complex containing tricyclohexyl phosphine;
Described single phosphine list N-heterocyclic carbine nickel (II) title complex containing tricyclohexyl phosphine is expressed by the following chemical structure formula:
，
In formula, Cy is cyclohexyl; R is the tertiary butyl, 2,6-diisopropyl phenyls or mesitylene base; X is chlorine or bromine.
2. preparation method according to claim 1, is characterized in that: in step [1], and described rare gas element is nitrogen or argon gas, and described solvent is not containing the solvent of reactive hydrogen.
3. preparation method according to claim 1, is characterized in that: in step [1], and the mol ratio of described single phosphine mono-quaternaries nickel (II) title complex, N-heterocyclic carbine, tricyclohexyl phosphine is (1 ~ 1.2): 1: 1.
4. preparation method according to claim 1, it is characterized in that: in step [1], under anhydrous and oxygen-free condition, in inert gas atmosphere, single phosphine mono-quaternaries nickel (II) title complex and N-heterocyclic carbine are dissolved in solvent, react 2 hours at 25 DEG C; Then add tricyclohexyl phosphine, then react 2 hours at 25 DEG C.
5. preparation method according to claim 1, is characterized in that: in step [2], adds normal hexane in the solution and carries out recrystallization.
6. single phosphine list N-heterocyclic carbine nickel (II) title complex containing tricyclohexyl phosphine carries out the application of cross-coupling reaction as single-component catalyst catalysis aryl grignard reagent and fragrant methyl ether; Described single phosphine list N-heterocyclic carbine nickel (II) title complex containing tricyclohexyl phosphine is expressed by the following chemical structure formula:
，
In formula, Cy is cyclohexyl; R is the tertiary butyl, 2,6-diisopropyl phenyls or mesitylene base; X is chlorine or bromine.
7. single phosphine list N-heterocyclic carbine nickel (II) title complex containing tricyclohexyl phosphine carries out the method for cross-coupling reaction as single component catalyst catalysis aryl grignard reagent and fragrant methyl ether, it is characterized in that, comprise the following steps: under anhydrous and oxygen-free condition, in inert gas atmosphere, under ice-water bath condition, catalyzer, tetrahydrofuran (THF), aryl grignard reagent and fragrant methyl ether are mixed, in 25 ~ 55 DEG C of stirring reactions 10 hours, uses deionized water termination reaction; Reactant through extraction, then through chromatography column separating-purifying, obtains product; Described single phosphine list N-heterocyclic carbine nickel (II) title complex containing tricyclohexyl phosphine is expressed by the following chemical structure formula:
，
In formula, Cy is cyclohexyl; R is the tertiary butyl, 2,6-diisopropyl phenyls or mesitylene base; X is chlorine or bromine.
8. method according to claim 7, is characterized in that: the mol ratio of fragrant methyl ether and aryl grignard reagent is 1: (1 ~ 2); The consumption of catalyzer is 1 ~ 5mol% of fragrant methyl ether.
9. method according to claim 8, is characterized in that: when fragrant methyl ether is naphthol methyl ether, and the mol ratio of aryl grignard reagent and naphthol methyl ether is 1.5: 1, and the consumption of catalyzer is the 1mol% of naphthol methyl ether, and temperature of reaction is 25 DEG C; When fragrant methyl ether is methyl-phenoxide, the mol ratio of aryl grignard reagent and methyl-phenoxide is 1.5: 1, and the consumption of catalyzer is the 5mol% of methyl-phenoxide, and temperature is 55 DEG C.
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