CN101284247B - Dinuclear nickel cross-coupling reaction catalyst supported by nitrogen heterocycle carbine ligand and preparation method thereof - Google Patents
Dinuclear nickel cross-coupling reaction catalyst supported by nitrogen heterocycle carbine ligand and preparation method thereof Download PDFInfo
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- CN101284247B CN101284247B CN2008100616751A CN200810061675A CN101284247B CN 101284247 B CN101284247 B CN 101284247B CN 2008100616751 A CN2008100616751 A CN 2008100616751A CN 200810061675 A CN200810061675 A CN 200810061675A CN 101284247 B CN101284247 B CN 101284247B
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000003446 ligand Substances 0.000 title claims abstract description 35
- 238000006880 cross-coupling reaction Methods 0.000 title claims abstract description 24
- 239000007809 chemical reaction catalyst Substances 0.000 title claims abstract description 22
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims description 45
- 229910052757 nitrogen Inorganic materials 0.000 title claims description 35
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 70
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000007787 solid Substances 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000002425 crystallisation Methods 0.000 claims abstract description 11
- 230000008025 crystallization Effects 0.000 claims abstract description 11
- 239000000706 filtrate Substances 0.000 claims abstract description 11
- 229910001923 silver oxide Inorganic materials 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000012141 concentrate Substances 0.000 claims description 20
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 150000002460 imidazoles Chemical class 0.000 claims description 5
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 4
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 3
- JGSLKNWXPRDWBA-UHFFFAOYSA-N 2-methylidene-1h-pyridine Chemical compound C=C1NC=CC=C1 JGSLKNWXPRDWBA-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- WUOIAOOSKMHJOV-UHFFFAOYSA-N ethyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(CC)C1=CC=CC=C1 WUOIAOOSKMHJOV-UHFFFAOYSA-N 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 238000007306 functionalization reaction Methods 0.000 claims description 2
- 150000003217 pyrazoles Chemical class 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 abstract description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 229910052763 palladium Inorganic materials 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 abstract 1
- 101150024701 PPH3 gene Proteins 0.000 abstract 1
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- 239000012847 fine chemical Substances 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 238000005481 NMR spectroscopy Methods 0.000 description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N DMSO Substances CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 16
- 239000000460 chlorine Substances 0.000 description 14
- 239000007868 Raney catalyst Substances 0.000 description 11
- 229910000564 Raney nickel Inorganic materials 0.000 description 11
- ZZLCFHIKESPLTH-UHFFFAOYSA-N 4-Methylbiphenyl Chemical group C1=CC(C)=CC=C1C1=CC=CC=C1 ZZLCFHIKESPLTH-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 238000003810 ethyl acetate extraction Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 229910002027 silica gel Inorganic materials 0.000 description 10
- 239000000741 silica gel Substances 0.000 description 10
- 229960001866 silicon dioxide Drugs 0.000 description 10
- 229910018106 Ni—C Inorganic materials 0.000 description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- QSSXJPIWXQTSIX-UHFFFAOYSA-N 1-bromo-2-methylbenzene Chemical compound CC1=CC=CC=C1Br QSSXJPIWXQTSIX-UHFFFAOYSA-N 0.000 description 6
- 239000007818 Grignard reagent Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 150000004795 grignard reagents Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- JQLWGNCKPUJSMY-UHFFFAOYSA-N 2-(2-methylphenyl)pyrimidine Chemical compound CC1=CC=CC=C1C1=NC=CC=N1 JQLWGNCKPUJSMY-UHFFFAOYSA-N 0.000 description 2
- MZGJUQSZWVIRFP-UHFFFAOYSA-N 3,5-bis(chloromethyl)-1h-pyrazole Chemical class ClCC=1C=C(CCl)NN=1 MZGJUQSZWVIRFP-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- YRGAYAGBVIXNAQ-UHFFFAOYSA-N 1-chloro-4-methoxybenzene Chemical compound COC1=CC=C(Cl)C=C1 YRGAYAGBVIXNAQ-UHFFFAOYSA-N 0.000 description 1
- RHDYQUZYHZWTCI-UHFFFAOYSA-N 1-methoxy-4-phenylbenzene Chemical group C1=CC(OC)=CC=C1C1=CC=CC=C1 RHDYQUZYHZWTCI-UHFFFAOYSA-N 0.000 description 1
- OUMKBAHMPRLISR-UHFFFAOYSA-N 1-phenyl-4-(trifluoromethyl)benzene Chemical group C1=CC(C(F)(F)F)=CC=C1C1=CC=CC=C1 OUMKBAHMPRLISR-UHFFFAOYSA-N 0.000 description 1
- 238000004009 13C{1H}-NMR spectroscopy Methods 0.000 description 1
- GRTWYIODJKVPEV-UHFFFAOYSA-N 2-(2-methylphenyl)pyridine Chemical compound CC1=CC=CC=C1C1=CC=CC=N1 GRTWYIODJKVPEV-UHFFFAOYSA-N 0.000 description 1
- OKDGRDCXVWSXDC-UHFFFAOYSA-N 2-chloropyridine Chemical compound ClC1=CC=CC=N1 OKDGRDCXVWSXDC-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- -1 chloro aryl compound Chemical class 0.000 description 1
- 230000002508 compound effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- QULYNCCPRWKEMF-UHFFFAOYSA-N parachlorobenzotrifluoride Chemical compound FC(F)(F)C1=CC=C(Cl)C=C1 QULYNCCPRWKEMF-UHFFFAOYSA-N 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a dual-core nickel cross-coupling reaction catalyst supported by N-heterocyclic carbine and a preparation method. Acetonitrile is taken as a solvent, N-heterocyclic carbine ligand and silver oxide in the molar ratio of 1: 3 to 1: 6 are added and stirred, the reaction is carried out for 10 to 15 hours away from light; Ni(DME)Cl2 or Ni(PPh3)2Cl2, Ni(DME)Cl2 or Ni(PPH3)2Cl2 and the N-heterocyclic carbine ligand in the molar ratio of 2: 1 to 3: 1 are added and filtered, the filtrate is condensed, ether is added for precipitation of yellow solids, the yellow solids are sequentially washed by ethanol and ether for 2 to 3 times, the acetonitrile is then used for dissolution, the ether is slowly added, and the dual-core nickel cross-coupling reaction catalyst supported by the N-heterocyclic carbine is obtained by crystallization. The dual-core nickel catalyst synthesized by the invention can play the synergy due to the shorter distance between two nickel atoms, the catalytic effect thereof is higher than the common palladium catalyst, thus having very ideal catalytic effect on chlorinated aryl compounds with cheap price and wide application prospect in fine chemical and pharmaceutical industries and being environment-friendly.
Description
Technical field
The present invention relates to dinuclear nickel cross-coupling reaction catalyst and preparation method that a kind of nitrogen heterocycle carbine ligand supports.
Background technology
Form the cross-coupling reaction such as the Suzuki of C-C key, Kumada etc. are reflected at industrial being with a wide range of applications, the catalyst of these cross-coupling reactions of catalysis the most widely of research is the Metal Palladium and the harmful phosphine part of environment of price comparison costliness at present, and this makes them be restricted aspect commercial Application.In recent years, as the replenishing and substituting of phosphine part, nitrogen heterocycle carbine ligand was widely used in (Jafarpour, L. in the various organic chemical reactionses; Nolan, S.P.J.Organomet.Chem, 2001,617-618,17-27), however, disclosed cross-coupling reaction catalyst with real value still uses Metal Palladium mostly, and all undesirable for the chloro aryl compound effect that is difficult to react.
Summary of the invention
The objective of the invention is to overcome the prior art deficiency, the dinuclear nickel cross-coupling reaction catalyst and the preparation method that provide a kind of nitrogen heterocycle carbine ligand to support.
The dinuclear nickel cross-coupling reaction catalyst that nitrogen heterocycle carbine ligand supports is that the N-heterocyclic carbine compound with the pyrazoles functionalization is a part, and with the hydroxyl bridging, its cationic molecule formula is between two nickle atoms:
Its anion is PF
6 -, Cl
-Perhaps BF
4 -
The molecular formula of described N-heterocyclic carbine compound is:
R represent methylidene pyridine wherein, pyridine, pyrimidine, methyldiphenyl base phosphorus, ethyl diphenylphosphine and derivative thereof.N-heterocyclic carbine (dotted line) is represented imidazoles, benzimidazole and derivative thereof.
Structural formula with the hydroxyl bridging between described two nickle atoms is:
The preparation method of the dinuclear nickel cross-coupling reaction catalyst that nitrogen heterocycle carbine ligand supports is: be solvent with the acetonitrile, adding mol ratio is 1: 3-1: 6 nitrogen heterocycle carbine ligand and silver oxide, stir lucifuge reaction 10-15 hour; Add Ni (DME) Cl
2Perhaps Ni (PPh
3)
2Cl
2, Ni (DME) Cl
2Perhaps Ni (PPh
3)
2Cl
2With the nitrogen heterocycle carbine ligand mol ratio be 2: 1-3: 1, filter, filtrate concentrates, add ether and separate out yellow solid, yellow solid is washed 2-3 time with ethanol, ether successively, with the acetonitrile dissolving, slowly add ether again, crystallization obtains the dinuclear nickel cross-coupling reaction catalyst that nitrogen heterocycle carbine ligand supports.
The double-core Raney nickel that the present invention synthesizes is owing to distance between two nickle atoms can play synergy than weak point, its catalytic effect is higher than common palladium catalyst, has very desirable catalytic effect for low-cost chloro aryl compound, and environmental friendliness, in fine chemistry industry and pharmaceuticals industry, be with a wide range of applications.
The specific embodiment
To help to understand the present invention by following examples of implementation, but not limit content of the present invention.
Embodiment 1,
At room temperature, add ligand L 1 702mg (1mmol), acetonitrile 20mL, silver oxide 696mg (3mmol) reacted 10 hours, added Ni (DME) Cl
2574mg (2mmol) filters, and filtrate concentrates, add ether and separate out yellow solid, yellow solid successively with ethanol, ether washing 2 times, is dissolved with acetonitrile again, slowly add ether, crystallization obtains the dinuclear nickel cross-coupling reaction catalyst 1 that the 424mg nitrogen heterocycle carbine ligand supports, productive rate 51%.
1H?NMR(400MHz，d
6-DMSO)：δ9.03(d，J＝5.6Hz，2H)，8.11(t，J＝7.6Hz，2H)，7.71(d，J＝5.6Hz，2H)，7.62(d，J＝2.0Hz，2H)，7.59(t，J＝6.4，7.6Hz，2H)，7.55(d，J＝2.0Hz，2H)，6.36(s，1H)，5.62(s，4H)，5.37(s，4H)，1.90(s，1H)ppm.
13C?NMR(400MHz，d
6-DMSO)：δ153.5(Ni-C)，152.0，149.7，145.4，140.7，125.4，125.3，123.1，123.1，102.4，52.4，46.6ppm.
Embodiment 2,
At room temperature, add ligand L 1702mg (1mmol), acetonitrile 20mL, silver oxide 1.392g (6mmol) reacted 10 hours, added Ni (DME) Cl
2574mg (2mmol) filters, and filtrate concentrates, add ether and separate out yellow solid, yellow solid successively with ethanol, ether washing 2 times, is dissolved with acetonitrile again, slowly add ether, crystallization obtains the dinuclear nickel cross-coupling reaction catalyst 1 that the 424mg nitrogen heterocycle carbine ligand supports, productive rate 51%.
1H?NMR(400MHz，d
6-DMSO)：δ9.03(d，J＝5.6Hz，2H)，8.11(t，J＝7.6Hz，2H)，7.71(d，J＝5.6Hz，2H)，7.62(d，J＝2.0Hz，2H)，7.59(t，J＝6.4，7.6Hz，2H)，7.55(d，J＝2.0Hz，2H)，6.36(s，1H)，5.62(s，4H)，5.37(s，4H)，1.90(s，1H)ppm.
13C?NMR(400MHz，d
6-DMSO)：δ153.5(Ni-C)，152.0，149.7，145.4，140.7，125.4，125.3，123.1，123.1，102.4，52.4，46.6ppm.
Embodiment 3,
At room temperature, add ligand L 1702mg (1mmol), acetonitrile 20mL, silver oxide 696g (3mmol) reacted 10 hours, added Ni (DME) Cl
2574mg (2mmol) filters, and filtrate concentrates, add ether and separate out yellow solid, yellow solid successively with ethanol, ether washing 3 times, is dissolved with acetonitrile again, slowly add ether, crystallization obtains the dinuclear nickel cross-coupling reaction catalyst 1 that the 424mg nitrogen heterocycle carbine ligand supports, productive rate 51%.
1H?NMR(400MHz，d
6-DMSO)：δ9.03(d，J＝5.6Hz，2H)，8.11(t，J＝7.6Hz，2H)，7.71(d，J＝5.6Hz，2H)，7.62(d，J＝2.0Hz，2H)，7.59(t，J＝6.4，7.6Hz，2H)，7.55(d，J＝2.0Hz，2H)，6.36(s，1H)，5.62(s，4H)，5.37(s，4H)，1.90(s，1H)ppm.
13C?NMR(400MHz，d
6-DMSO)：δ153.5(Ni-C)，152.0，149.7，145.4，140.7，125.4，125.3，123.1，123.1，102.4，52.4，46.6ppm.
Embodiment 4,
At room temperature, add ligand L 1702mg (1mmol), acetonitrile 20mL, silver oxide 1.392g (6mmol) reacted 10 hours, added Ni (PPh
3)
2Cl
21.308g (2mmol), filter, filtrate concentrates, add ether and separate out yellow solid, yellow solid successively with ethanol, ether washing 2 times, is dissolved with acetonitrile again, slowly add ether, crystallization obtains the dinuclear nickel cross-coupling reaction catalyst 1 that the 441mg nitrogen heterocycle carbine ligand supports, productive rate 53%.
1H?NMR(400MHz，d
6-DMSO)：δ9.03(d，J＝5.6Hz，2H)，8.11(t，J＝7.6Hz，2H)，7.71(d，J＝5.6Hz，2H)，7.62(d，J＝2.0Hz，2H)，7.59(t，J＝6.4，7.6Hz，2H)，7.55(d，J＝2.0Hz，2H)，6.36(s，1H)，5.62(s，4H)，5.37(s，4H)，1.90(s，1H)ppm.
13CNMR(400MHz，d
6-DMSO)：δ153.5(Ni-C)，152.0，149.7，145.4，140.7，125.4，125.3，123.1，123.1，102.4，52.4，46.6ppm.
Embodiment 5,
At room temperature, add ligand L 1702mg (1mmol), acetonitrile 20mL, silver oxide 696mg (3mmol) reacted 15 hours, added Ni (DME) Cl
2574mg (2mmol) filters, and filtrate concentrates, add ether and separate out yellow solid, yellow solid successively with ethanol, ether washing 2 times, is dissolved with acetonitrile again, slowly add ether, crystallization obtains the dinuclear nickel cross-coupling reaction catalyst 1 that the 424mg nitrogen heterocycle carbine ligand supports, productive rate 51%.
1H?NMR(400MHz，d
6-DMSO)：δ9.03(d，J＝5.6Hz，2H)，8.11(t，J＝7.6Hz，2H)，7.71(d，J＝5.6Hz，2H)，7.62(d，J＝2.0Hz，2H)，7.59(t，J＝6.4，7.6Hz，2H)，7.55(d，J＝2.0Hz，2H)，6.36(s，1H)，5.62(s，4H)，5.37(s，4H)，1.90(s，1H)ppm.
13C?NMR(400MHz，d
6-DMSO)：δ153.5(Ni-C)，152.0，149.7，145.4，140.7，125.4，125.3，123.1，123.1，102.4，52.4，46.6ppm.
Embodiment 6,
At room temperature, add ligand L 1702mg (1mmol), acetonitrile 20mL, silver oxide 696mg (3mmol) reacted 15 hours, added Ni (DME) Cl
2861mg (3mmol) filters, and filtrate concentrates, add ether and separate out yellow solid, yellow solid successively with ethanol, ether washing 2 times, is dissolved with acetonitrile again, slowly add ether, crystallization obtains the dinuclear nickel cross-coupling reaction catalyst 1 that the 433mg nitrogen heterocycle carbine ligand supports, productive rate 52%.
1H?NMR(400MHz，d
6-DMSO)：δ9.03(d，J＝5.6Hz，2H)，8.11(t，J＝7.6Hz，2H)，7.71(d，J＝5.6Hz，2H)，7.62(d，J＝2.0Hz，2H)，7.59(t，J＝6.4，7.6Hz，2H)，7.55(d，J＝2.0Hz，2H)，6.36(s，1H)，5.62(s，4H)，5.37(s，4H)，1.90(s，1H)ppm.
13C?NMR(400MHz，d
6-DMSO)：δ153.5(Ni-C)，152.0，149.7，145.4，140.7，125.4，125.3，123.1，123.1，102.4，52.4，46.6ppm.
Embodiment 7,
At room temperature, add ligand L 2674mg (1mmol), acetonitrile 20mL, silver oxide 696mg (3mmol) reacted 15 hours, added Ni (DME) Cl
2574mg (2mmol) filters, and filtrate concentrates, add ether and separate out yellow solid, yellow solid successively with ethanol, ether washing 2 times, is dissolved with acetonitrile again, slowly add ether, crystallization obtains the dinuclear nickel cross-coupling reaction catalyst 2 that the 371mg nitrogen heterocycle carbine ligand supports, productive rate 46%.
1H?NMR(400MHz，d
6-DMSO)：δ8.35(s，2H)，8.34(m，4H)，7.98(d，J＝8.0Hz，2H)，7.69(s，2H)，7.56(t，J＝6.4Hz，2H)，6.38(s，1H)，5.45(s，4H)，1.67(s，1H)ppm.
13C?NMR(400MHz，d
6-DMSO)：δ157.9(Ni-C)，150.2，150.1，144.9，144.0，124.2，123.3，118.5，111.8，103.3，47.8ppm.
Embodiment 8,
At room temperature, add ligand L 2674mg (1mmol), acetonitrile 20mL, silver oxide 696mg (3mmol) reacted 15 hours, added Ni (PPh
3)
2Cl
21.306mg (2mmol), filter, filtrate concentrates, add ether and separate out yellow solid, yellow solid successively with ethanol, ether washing 2 times, with the acetonitrile dissolving, is slowly added ether again, crystallization obtains the dinuclear nickel cross-coupling reaction catalyst 2 that the 387mg nitrogen heterocycle carbine ligand supports, productive rate 46%.
1H?NMR(400MHz，d
6-DMSO)：δ8.35(s，2H)，8.34(m，4H)，7.98(d，J＝8.0Hz，2H)，7.69(s，2H)，7.56(t，J＝6.4Hz，2H)，6.38(s，1H)，5.45(s，4H)，1.67(s，1H)ppm.
13CNMR(400MHz，d
6-DMSO)：δ157.9(Ni-C)，150.2，150.1，144.9，144.0，124.2，123.3，118.5，111.8，103.3，47.8ppm.
Embodiment 9,
2-imidazoles picoline 795mg (5mmol), 3,5-dichloromethyl pyrazoles 330mg (2mmol), in acetone solvent, refluxed 10 hours, and obtained yellow sticky solid, with twice of this solid of toluene wash, be dissolved in again in the 10mL water, the aqueous solution of above-mentioned imidazole salts is added drop-wise to 1g NH
4PF
6The aqueous solution in, filter, use ethanol, ether washed twice respectively, obtain yellow solid 805mg, productive rate 57%.
1H?NMR(400MHz，DMSO-d
6)：13.45(s，1H，NH)，9.34(s，2H，NCHN)，8.54(d，J＝4.8，2H，6-py)，7.90(t，J＝7.6，2H，4-py)，7.80，7.75(s，each?2H，CHi
mdazole)，7.49(d，J＝7.2，2H，3-py)，7.41(t，J＝4.8，7.2，2H，5-py)，6.48(s，1H，CH
pyrazole)，5.58-5.40(m，8H，CH
2).?
13C{
1H}NMR(100.6MHz，DMSO-d
6)：153.8，153.7，149.9，147.2，137.9，137.8，137.6，137.3，128.2，124.1，124.0，123.9，123.8，123.7，122.9，122.7，105.5，53.4，48.8.
Embodiment 10,
2-Imidazopyridine 725mg (5mmol), 3,5-dichloromethyl pyrazoles 330mg (2mmol), in acetone solvent, refluxed 10 hours, and obtained white sticky solid, with twice of this solid of toluene wash, be dissolved in again in the 10mL water, the aqueous solution of above-mentioned imidazole salts is added drop-wise to 1g NH
4PF
6The aqueous solution in, filter, use ethanol, ether washed twice respectively, obtain white solid 608mg, productive rate 47%.
Embodiment 11,
Under nitrogen protection, in reaction tube, add 0.8mg (0.1%mmol) double-core Raney nickel 1, chlorobenzene 101 μ L (1mmol), the grignard reagent 1.2mmol of methyl bromobenzene, room temperature reaction 10 hours adds dilute hydrochloric acid solution 10mL, uses ethyl acetate extraction, uses MgSO
4Drying concentrates again, crosses silicagel column and separates (leacheate benzinum), obtains product 4-methyl biphenyl, productive rate: 129mg (77%).
1H?NMR(400MHz，CDCl
3，TMS)：δ7.57(d，J＝8.0Hz，2H)，7.49(d，J＝8.0Hz，2H)，7.43(t，J＝7.6Hz，2H)，7.32(t，J＝7.6Hz，1H)，7.24(t，J＝7.6Hz，2H)，2.38(s，3H)ppm.MS(EI，m/z)：168[M
+].
Embodiment 12,
Under nitrogen protection, in reaction tube, add 4mg (0.5%mmol) double-core Raney nickel 1, chlorobenzene 101 μ L (1mmol), the grignard reagent 1.2mmol of methyl bromobenzene, room temperature reaction 10 hours adds dilute hydrochloric acid solution 10mL, uses ethyl acetate extraction, uses MgSO
4Drying concentrates again, crosses silicagel column and separates (leacheate benzinum), obtains product 4-methyl biphenyl, productive rate: 168mg (100%).
1H?NMR(400MHz，CDCl
3，TMS)：δ7.57(d，J＝8.0Hz，2H)，7.49(d，J＝8.0Hz，2H)，7.43(t，J＝7.6Hz，2H)，7.32(t，J＝7.6Hz，1H)，7.24(t，J＝7.6Hz，2H)，2.38(s，3H)ppm.MS(EI，m/z)：168[M
+].
Embodiment 13,
Under nitrogen protection, in reaction tube, add 4mg (0.5%mmol) double-core Raney nickel 1,2-chloropyridine 120 μ L (1mmol); the grignard reagent 1.2mmol of methyl bromobenzene, room temperature reaction 10 hours adds dilute hydrochloric acid solution 10mL; use ethyl acetate extraction, use MgSO
4Drying concentrates again, crosses silicagel column and separates (leacheate benzinum), obtains product 2-tolyl pyridine, productive rate: 169mg (100%).
1H?NMR(400MHz，CDCl
3，TMS)：δ8.66(d，J＝4.4Hz，1H)，7.89(d，J＝8.0Hz，2H)，7.70(m，2H)，7.28(d，J＝8.0Hz，2H)，7.17(m，1H)，2.39(s，3H)ppm.MS(EI，m/z)：169[M
+].
Embodiment 14,
Under nitrogen protection, in reaction tube, add 4mg (0.5%mmol) double-core Raney nickel 1,2-chlorine pyrimidine 114mg (1mmol), the grignard reagent 1.2mmol of methyl bromobenzene, room temperature reaction 10 hours adds dilute hydrochloric acid solution 10mL, uses ethyl acetate extraction, uses MgSO
4Drying concentrates again, crosses silicagel column and separates (leacheate benzinum), obtains product 2-tolyl pyrimidine, productive rate: 170mg (100%).
1H?NMR(400MHz，CDCl
3，TMS)：δ8.78(d，J＝4.8Hz，2H)，8.34(d，J＝8.0Hz，2H)，7.31(d，J＝8.0Hz，2H)，7.15(d，J＝4.8Hz，1H)，2.42(s，3H)ppm.MS(EI，m/z)：170[M
+]
Embodiment 15,
Under nitrogen protection, in reaction tube, add 4mg (0.5%mmol) double-core Raney nickel 1,4-chloroanisole 142mg (1mmol); the grignard reagent 1.2mmol of methyl bromobenzene, room temperature reaction 10 hours adds dilute hydrochloric acid solution 10mL; use ethyl acetate extraction, use MgSO
4Drying concentrates again, crosses silicagel column and separates (leacheate benzinum), obtains product 2-tolyl pyrimidine, productive rate: 194mg (98%).
1H?NMR(400MHz，CDCl
3，TMS)：δ7.51(d，J＝8.4Hz，2H)，7.45(d，J＝8.4HZ，2H)，7.24(m，2H)，6.97(d，J＝8.8Hz，2H)，3.84(s，3H)，2.37(s，3H)ppm.MS(EI，m/z)：199[M
+]
Embodiment 16,
Under nitrogen protection, in reaction tube, add 0.8mg (0.1%mmol) double-core Raney nickel 2, chlorobenzene 101 μ L (1mmol), the grignard reagent 1.2mmol of methyl bromobenzene, room temperature reaction 10 hours adds dilute hydrochloric acid solution 10mL, uses ethyl acetate extraction, uses MgSO
4Drying concentrates again, crosses silicagel column and separates (leacheate benzinum), obtains product 4-methyl biphenyl, productive rate: 129mg (77%).
1H?NMR(400MHz，CDCl
3，TMS)：δ7.57(d，J＝8.0Hz，2H)，7.49(d，J＝8.0Hz，2H)，7.43(t，J＝7.6HZ，2H)，7.32(t，J＝7.6HZ，1H)，7.24(t，J＝7.6Hz，2H)，2.38(s，3H)ppm.MS(EI，m/z)：168[M
+].
Embodiment 17,
Under nitrogen protection, in reaction tube, add 1.6mg (0.2%mmol) double-core Raney nickel 1,2.6mg (1%mmol) triphenylphosphine, 4-methyl chlorobenzene 120 μ L (1mmol), phenyl boric acid 145mg (1.2mmol), K
3PO
4422mg (2mmol), 3mL toluene, 80 ℃ were reacted 3 hours, added entry 10mL to reactant liquor, used ethyl acetate extraction, used MgSO
4Drying concentrates again, crosses silicagel column and separates (leacheate benzinum), obtains product 4-methyl biphenyl, productive rate: 164mg (98%).
1H?NMR(400MHz，CDCl
3，TMS)：δ7.57(d，J＝8.0Hz，2H)，7.49(d，J＝8.0Hz，2H)，7.43(t，J＝7.6Hz，2H)，7.32(t，J＝7.6Hz，1H)，7.24(t，J＝7.6Hz，2H)，2.38(s，3H)ppm.MS(EI，m/z)：168[M
+].
Embodiment 18,
Under nitrogen protection, in reaction tube, add 1.6mg (0.2%mmol) double-core Raney nickel 2,2.6mg (1%mmol) triphenylphosphine, 4-methyl chlorobenzene 120 μ L (1mmol), phenyl boric acid 145mg (1.2mmol), K
3PO
4422mg (2mmol), 3mL toluene, 80 ℃ were reacted 3 hours, added entry 10mL to reactant liquor, used ethyl acetate extraction, used MgSO
4Drying concentrates again, crosses silicagel column and separates (leacheate benzinum), obtains product 4-methyl biphenyl, productive rate: 164mg (98%).
1H?NMR(400MHz，CDCl
3，TMS)：δ7.57(d，J＝8.0Hz，2H)，7.49(d，J＝8.0Hz，2H)，7.43(t，J＝7.6Hz，2H)，7.32(t，J＝7.6Hz，1H)，7.24(t，J＝7.6Hz，2H)，2.38(s，3H)ppm.MS(EI，m/z)：168[M
+].
Embodiment 19,
Under nitrogen protection, in reaction tube, add 1.6mg (0.2%mmol) double-core Raney nickel 1,2.6mg (1%mmol) triphenylphosphine, 4-trifluoromethyl chlorobenzene 180mg (1mmol), phenyl boric acid 145mg (1.2mmol), K
3PO
4422mg (2mmol), 3mL toluene, 80 ℃ were reacted 3 hours, added entry 10mL to reactant liquor, used ethyl acetate extraction, used MgSO
4Drying concentrates again, crosses silicagel column and separates (leacheate benzinum), obtains product 4-trifluoromethyl-biphenyl, productive rate: 200mg (100%).
1H?NMR(400MHz，CDCl
3，TMS)：δ7.68(s，4H)，7.59(d，J＝7.2Hz，2H)，7.48(t，J＝7.2Hz，2H)，7.41(t，J＝7.2Hz，1H)ppm.MS(EI，m/z)：222[M
+]
Embodiment 20,
Under nitrogen protection, in reaction tube, add 1.6mg (0.2%mmol) double-core Raney nickel 1,2.6mg (1%mmol) triphenylphosphine, 4-methoxyl group chlorobenzene 142mg (1mmol), phenyl boric acid 145mg (1.2mmol), K
3PO
4422mg (2mmol), 3mL toluene, 80 ℃ were reacted 3 hours, added entry 10mL to reactant liquor, used ethyl acetate extraction, used MgSO
4Drying concentrates again, crosses silicagel column and separates (leacheate benzinum), obtains product 4-methoxyl biphenyl, productive rate: 180mg (98%).
1H?NMR(400MHz，CDCl
3，TMS)：δ?7.55(m，4H)，7.43(m，2H)，7.31(m，1H)，6.98(d，J＝8.4Hz，2H)，3.85(s，3H)ppm.MS(EI，m/z)：184[M
+].
Claims (3)
1. the dinuclear nickel cross-coupling reaction catalyst that nitrogen heterocycle carbine ligand supports is characterized in that the N-heterocyclic carbine compound with the pyrazoles functionalization is a part, and with the hydroxyl bridging, its cationic molecule formula is between two nickle atoms:
Wherein, R represent methylidene pyridine, pyridine, pyrimidine, methyldiphenyl base phosphorus, ethyl diphenylphosphine and derivative thereof, the dotted line in the N-heterocyclic carbine molecular formula is represented imidazoles, and benzimidazole and derivative thereof, anion are PF
6 -, Cl
-Perhaps BF
4 -
2. according to the dinuclear nickel cross-coupling reaction catalyst of the described a kind of nitrogen heterocycle carbine ligand support of claim 1, it is characterized in that the molecular formula of described nitrogen heterocycle carbine ligand is:
R represent methylidene pyridine wherein, pyridine, pyrimidine, methyldiphenyl base phosphorus, ethyl diphenylphosphine and derivative thereof, the dotted line in the N-heterocyclic carbine molecular formula is represented imidazoles, benzimidazole and derivative thereof.
3. preparation method of the dinuclear nickel cross-coupling reaction catalyst that supports of nitrogen heterocycle carbine ligand according to claim 1, it is characterized in that: be solvent with the acetonitrile, adding mol ratio is 1: 3-1: 6 nitrogen heterocycle carbine ligand and silver oxide, stir lucifuge reaction 10-15 hour; Add Ni (DME) Cl
2Perhaps Ni (PPh
3)
2Cl
2, Ni (DME) Cl
2Perhaps Ni (PPh
3)
2Cl
2With the nitrogen heterocycle carbine ligand mol ratio be 2: 1-3: 1, filter, filtrate concentrates, add ether and separate out yellow solid, yellow solid is washed 2-3 time with ethanol, ether successively, with the acetonitrile dissolving, slowly add ether again, crystallization obtains the dinuclear nickel cross-coupling reaction catalyst that nitrogen heterocycle carbine ligand supports.
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