CN104341457A - 一种1,2,3-三唑功能化氮杂环卡宾双核镍化合物及其制备方法 - Google Patents
一种1,2,3-三唑功能化氮杂环卡宾双核镍化合物及其制备方法 Download PDFInfo
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- CN104341457A CN104341457A CN201410568265.1A CN201410568265A CN104341457A CN 104341457 A CN104341457 A CN 104341457A CN 201410568265 A CN201410568265 A CN 201410568265A CN 104341457 A CN104341457 A CN 104341457A
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- nickel compound
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- triazole
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- 150000002816 nickel compounds Chemical class 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 title claims abstract description 9
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 title abstract description 8
- 239000003446 ligand Substances 0.000 claims abstract description 27
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical group C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 10
- 238000007306 functionalization reaction Methods 0.000 claims description 51
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 150000000177 1,2,3-triazoles Chemical class 0.000 claims description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 31
- 229910052757 nitrogen Inorganic materials 0.000 claims description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- SYOANZBNGDEJFH-UHFFFAOYSA-N 2,5-dihydro-1h-triazole Chemical compound C1NNN=C1 SYOANZBNGDEJFH-UHFFFAOYSA-N 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 11
- 150000002460 imidazoles Chemical class 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052759 nickel Inorganic materials 0.000 abstract description 10
- -1 nickel carbene compound Chemical class 0.000 abstract description 10
- 150000001875 compounds Chemical class 0.000 abstract description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 125000002524 organometallic group Chemical group 0.000 abstract description 4
- 238000006880 cross-coupling reaction Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract 2
- 239000012847 fine chemical Substances 0.000 abstract 1
- 125000002883 imidazolyl group Chemical group 0.000 abstract 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000006555 catalytic reaction Methods 0.000 description 11
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N DMSO Substances CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 239000007818 Grignard reagent Substances 0.000 description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- QSSXJPIWXQTSIX-UHFFFAOYSA-N 1-bromo-2-methylbenzene Chemical compound CC1=CC=CC=C1Br QSSXJPIWXQTSIX-UHFFFAOYSA-N 0.000 description 6
- 150000008422 chlorobenzenes Chemical class 0.000 description 6
- 150000004795 grignard reagents Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- ZZLCFHIKESPLTH-UHFFFAOYSA-N 4-Methylbiphenyl Chemical group C1=CC(C)=CC=C1C1=CC=CC=C1 ZZLCFHIKESPLTH-UHFFFAOYSA-N 0.000 description 5
- 229910018106 Ni—C Inorganic materials 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000010898 silica gel chromatography Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- 238000012650 click reaction Methods 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 150000003217 pyrazoles Chemical class 0.000 description 3
- 125000001399 1,2,3-triazolyl group Chemical group N1N=NC(=C1)* 0.000 description 2
- OKDGRDCXVWSXDC-UHFFFAOYSA-N 2-chloropyridine Chemical compound ClC1=CC=CC=N1 OKDGRDCXVWSXDC-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- CLWRFNUKIFTVHQ-UHFFFAOYSA-N [N].C1=CC=NC=C1 Chemical group [N].C1=CC=NC=C1 CLWRFNUKIFTVHQ-UHFFFAOYSA-N 0.000 description 2
- 150000001500 aryl chlorides Chemical class 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- PFIADAMVCJPXSF-UHFFFAOYSA-N chloroneb Chemical compound COC1=CC(Cl)=C(OC)C=C1Cl PFIADAMVCJPXSF-UHFFFAOYSA-N 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 230000002153 concerted effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N phenyl bromide Natural products BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RHDYQUZYHZWTCI-UHFFFAOYSA-N 1-methoxy-4-phenylbenzene Chemical group C1=CC(OC)=CC=C1C1=CC=CC=C1 RHDYQUZYHZWTCI-UHFFFAOYSA-N 0.000 description 1
- NJWIMFZLESWFIM-UHFFFAOYSA-N 2-(chloromethyl)pyridine Chemical compound ClCC1=CC=CC=N1 NJWIMFZLESWFIM-UHFFFAOYSA-N 0.000 description 1
- PEPGFUNLRPSYHI-UHFFFAOYSA-O C(c1c[n](Cc2ccccc2)nn1)N1C=C[NH+](Cc2ccccn2)C1 Chemical compound C(c1c[n](Cc2ccccc2)nn1)N1C=C[NH+](Cc2ccccn2)C1 PEPGFUNLRPSYHI-UHFFFAOYSA-O 0.000 description 1
- CGBJKNGYTPUSAO-VXBULBDJSA-O CCCCN/C=C(/C[N+]1(C=CN(Cc2ncccc2)C1)[O-])\N=[NH2+] Chemical compound CCCCN/C=C(/C[N+]1(C=CN(Cc2ncccc2)C1)[O-])\N=[NH2+] CGBJKNGYTPUSAO-VXBULBDJSA-O 0.000 description 1
- 238000006411 Negishi coupling reaction Methods 0.000 description 1
- 241000144722 Parasa mirza Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- UDLLFLQFQMACJB-UHFFFAOYSA-N azidomethylbenzene Chemical compound [N-]=[N+]=NCC1=CC=CC=C1 UDLLFLQFQMACJB-UHFFFAOYSA-N 0.000 description 1
- ZIQCCIAIROIHHR-UHFFFAOYSA-N benzene;boric acid Chemical class OB(O)O.C1=CC=CC=C1 ZIQCCIAIROIHHR-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/325—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a metal atom
- C07C1/326—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a metal atom the hetero-atom being a magnesium atom
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/127—Preparation from compounds containing pyridine rings
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- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
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Abstract
本发明涉及一种1,2,3-三唑功能化氮杂环卡宾双核镍化合物及其制备方法,属于金属有机化学领域。一种1,2,3-三唑功能化氮杂环卡宾双核镍化合物是以1,2,3-三唑功能化的氮杂环卡宾为配体,氮杂环卡宾与镍的摩尔比为1:1,其分子结构式为:其中R1为咪唑或苯并咪唑,R2为苄基或正丁基或苯基中的一种;X为PF6或BF4中的一种。1,2,3-三唑功能化氮杂环卡宾双核镍化合物制备方法简单,双核镍卡宾化合物对空气和湿气稳定,镍原子之间距离较短,具有金属-金属间作用,利用该类催化剂,可以高效的实现交叉偶联反应,以高于90%的收率得到多种联苯衍生物,具有很好的官能团兼容性,环境友好,可广泛的应用于精细化工和制药工业中。
Description
技术领域
本发明涉及一种1,2,3-三唑功能化氮杂环卡宾双核镍化合物及其制备方法,属于金属有机化学技术领域。
背景技术
近几年来,氮杂环卡宾配体由于其独特的电子性能比较膦配体更高的对热和空气的稳定性,已经被作为膦配体的补充和替代,广泛应用于催化各种有机化学反应中,尤其是双金属化合物优越的催化性能,使得其受到了很大的关注(Korbinian Riener,Stefan Haslinger,Andreas Raba,Manuel P.Mirza Cokoja,Wolfgang A.Herrmann,and Fritz E.Kühn,Chemistry of Iron N-HeterocyclicCarbene Complexes:Syntheses,Structures,Reactivities,and Catalytic Applications,Chem.Rev.,2014,114,5215–5272;Diez-Gonzalez,S.,Marion,N.,and Nolan,S.P.N-Heterocyclic Carbenes in Late Transition Metal Catalysis,Chem.Rev.,2009,109,3612-3676)。尽管如此,在已经公开的报道中,氮杂环卡宾支撑的双核镍化合物的研究仍然很少(中国专利CN201110241732,Zhou Y,Xi Z,Chen W,Wang D.,Dinickel(II)Complexes of Bis(N-heterocyclic carbene)Ligands Containing[Ni2(μ-OH)]Cores as Highly Efficient Catalysts for the Coupling of Aryl Chlorides,Organometallics,2008,27,5911-5920;Xi Z,Zhou Y,Chen W.,Efficient NegishiCoupling Reactions of Aryl Chlorides Catalyzed by Binuclear and MononuclearNickel-N-Heterocyclic Carbene Complexes,The Journal of Organic Chemistry,2008,73,8497-8501),然而上述报道的双核镍卡宾化合物仅限于吡唑功能化化合物,1,2,3-三唑功能化氮杂环卡宾双核镍化合物的制备及其在催化交叉偶联反应中的应用还未见报道。双核金属化合物由于金属-金属间的相互作用,能够在催化反应过程中起到协同催化作用,从而显著地提高催化剂的催化活性,因此简单方便地制备对空气和水汽有很好稳定性的氮杂环卡宾双核镍化合物,实现温和条件下,高效的催化交叉偶联反应,在工业上具有广泛的应用前景。
发明内容
针对上述不足,本发明的目的在于提供一种在镍催化的交叉偶联反应中具有高效催化活性的1,2,3-三唑功能化氮杂环卡宾双核镍化合物及其制备方法,为实现上述目的,本发明的技术解决方案是:
一种1,2,3-三唑功能化氮杂环卡宾双核镍化合物,所述1,2,3-三唑功能化氮杂环卡宾双核镍化合物的分子结构式I为:
其中R1为咪唑或苯并咪唑,R2为苄基或正丁基或苯基中的一种。
X为PF6或BF4中的一种。
将1,2,3-三唑功能化氮杂环卡宾配体和氧化银以2:1的摩尔比加入到盛有1,2,3-三唑功能化氮杂环卡宾配体质量50倍乙腈的Schlenk反应管内,其中所述1,2,3-三唑功能化氮杂环卡宾配体的分子结构式II为:
其中R1为咪唑或苯并咪唑,R2为苄基或正丁基或苯基中的一种;X为PF6或BF4中的一种;空气氛围中,50℃下,避光搅拌反应10-15小时;随后,加入与1,2,3-三唑功能化氮杂环卡宾配体摩尔比为1:1的NiCl2(PPh3)2,在25℃下搅拌反应5-10小时;离心过滤掉沉淀物,浓缩滤液,加入浓缩液10倍体积的无水乙醚,析出固体,过滤收集固体,30℃下真空干燥10h,得到分子结构式为I
的1,2,3-三唑功能化氮杂环卡宾双核镍化合物。
其中,R1为咪唑或苯并咪唑,
R2为苄基或正丁基或苯基中的一种,
X为PF6或BF4中的一种。
由于采用以上技术方案,本发明具有以下优点:
氮杂环卡宾给电子能力强、易于制备、易官能化而且环境友好等特点成为金属有机化学领域的研究热点,氮杂环卡宾过渡金属化合物在均相催化领域已经取得了很大地成功,而1,2,3-三唑作为常见的杂环化合物配体,在金属化合物中可以作为辅助配体参与络合,同时1,2,3-三唑功能化的氮杂环卡宾前体可以方便的通过铜催化的点击反应制备,相对于吡唑桥连的双金属卡宾镍化合物,和已有的技术方法相比,反应步骤简单,得到化合物的结构新颖,产率高,适合于大规模制备。本发明结合1,2,3-三唑弱配位的特点以及氮杂环卡宾的优点通过铜催化的点击反应制备了1,2,3-三唑功能化的氮杂环卡宾配体,并经过简单的银卡宾金属交换反应制备了1,2,3-三唑功能化氮杂环卡宾双核镍化合物。在双核镍化合物中,由于1,2,3-三唑的特殊的电子性能,得到了每个镍原子同时和一个吡啶氮原子、一个1,2,3-三唑氮原子、一个卡宾碳原子配位,并与另外的镍原子通过羟基桥连形成了双核镍卡宾化合物。
利用1,2,3-三唑功能化氮杂环卡宾双核镍为催化剂,25℃下,可以使取代氯苯衍生物与溴苯格氏试剂反应形成联苯衍生物,可用下式表示:
其中,R3为氢原子或吡啶基或甲基或甲氧基,R4为甲基或甲氧基。
溴苯格氏试剂衍生物与氯苯衍生物的摩尔比为1.2:1,1,2,3-三唑功能化氮杂环卡宾双核镍化合物相对于氯苯衍生物的用量为0.5mol%,反应的时间为3~12小时。
利用1,2,3-三唑功能化氮杂环卡宾双核镍为催化剂,80℃下,可以使取代氯苯衍生物与取代苯硼酸反应形成联苯衍生物,可用下式表示:
其中,R3为氢原子或吡啶基或甲基或甲氧基,R4为甲基或甲氧基。
取代苯硼酸与氯苯衍生物的摩尔比为1.2:1,1,2,3-三唑功能化氮杂环卡宾双核镍化合物相对于氯苯衍生物的用量为0.2mol%,反应的时间为2~4小时。
双核镍卡宾化合物的制备利用简单方便的金属交换反应得到,无需无水无氧操作,制备方法简单,设备要求低,操作控制方便,产率高,易于实现工业化生产。双核镍卡宾化合物对空气和湿气稳定,由于镍原子之间距离较短,具有金属-金属间作用,利用该类催化剂,可以高效的实现交叉偶联反应,以高于90%的收率得到多种联苯衍生物,具有很好的官能团兼容性,显示出了很好的协同催化作用,催化反应条件温和,催化效率高,环境友好,在精细化工和制药工业中具有广泛的应用前景。
具体实施方式
以下结合具体实施例对本发明做进一步的描述。
一种1,2,3-三唑功能化氮杂环卡宾双核镍化合物,所述1,2,3-三唑功能化氮杂环卡宾双核镍化合物的分子结构式I为:
其中R1为咪唑或苯并咪唑,R2为苄基或正丁基或苯基中的一种。
X为PF6或BF4中的一种。
将1,2,3-三唑功能化氮杂环卡宾配体和氧化银以2:1的摩尔比加入到盛有1,2,3-三唑功能化氮杂环卡宾配体质量50倍乙腈的Schlenk反应管内,其中所述1,2,3-三唑功能化氮杂环卡宾配体的分子结构式II为:
其中R1为咪唑或苯并咪唑,R2为苄基或正丁基或苯基中的一种;X为PF6或BF4中的一种;空气氛围中,50℃下,避光搅拌反应10-15小时;随后,加入与1,2,3-三唑功能化氮杂环卡宾配体摩尔比为1:1的NiCl2(PPh3)2,在25℃下搅拌反应5-10小时;离心过滤掉沉淀物,浓缩滤液,加入浓缩液10倍体积的无水乙醚,析出固体,过滤收集固体,30℃下真空干燥10h,得到分子结构式为I
的1,2,3-三唑功能化氮杂环卡宾双核镍化合物;
其中,R1为咪唑或苯并咪唑,
R2为苄基或正丁基或苯基中的一种。
X为PF6或BF4中的一种。
由于采用了以上技术方案,本发明所使用1,2,3-三唑功能化氮杂环卡宾配体和双金属卡宾镍化合物容易制备,在空气中稳定,和已有的技术方法相比,配体采用铜催化的点击反应在水相中制备得到,制备方法简单,电子和立体性能易于调节,品种多样。相对于吡唑桥连的双金属卡宾镍化合物,和已有的技术方法相比,反应步骤简单,得到化合物的结构新颖,产率高,适合于大规模制备。本发明结合1,2,3-三唑弱配位的特点以及氮杂环卡宾的优点通过铜催化的点击反应制备了1,2,3-三唑功能化的氮杂环卡宾配体,并经过简单的银卡宾金属交换反应制备了1,2,3-三唑功能化氮杂环卡宾双核镍化合物。在双核镍化合物中,由于1,2,3-三唑配体特殊的电子和空间性能,得到了每个镍原子同时和一个吡啶氮原子、一个1,2,3-三唑氮原子、一个卡宾碳原子配位,并与另外的镍原子通过羟基桥连形成了双核镍卡宾化合物。制备本发明化合物的起始物质正丁基叠氮、苯基叠氮、苄基叠氮、2-氯甲基吡啶、3-溴丙炔,咪唑、苯并咪唑等均可以从市场上买到或容易地通过已知的方法制得,所有用于合成和分析的试剂都是分析纯,并没有经过进一步的处理。
具体实施例
实施例1
50℃下,在Schlenk反应管内加入1,2,3-三唑功能化氮杂环卡宾配体L1(477mg,1mmol),氧化银(116mg,0.5mmol)和乙腈20mL,反应10小时,随后加入NiCl2(PPh3)2(654mg,1mmol),在25℃下搅拌反应6小时,离心过滤掉沉淀物,滤液浓缩至2mL,加入20mL无水乙醚,析出固体,过滤收集固体,30℃下真空干燥10h,得到分子结构式为1的1,2,3-三唑功能化氮杂环卡宾双核镍化合物700mg,产率55%。1H NMR(400MHz,d6-DMSO):δ8.54(b,1H),8.30(s,1H),7.89(t,J=7.2Hz,1H),7.79(s,2H),7.48(d,J=7.6Hz,1H),7.39-7.33(m,6H),5.64(s,2H),5.68(s,4H)ppm.13C NMR(400MHz,d6-DMSO):δ156.9(Ni-C),153.9,150.1,141.2,138.0,137.5,136.2,129.3,128.8,125.1,124.2,123.9,123.1,123.0,53.6,53.5,44.2ppm.
利用上述步骤得到的分子结构式为1的1,2,3-三唑功能化氮杂环卡宾双核镍化合物为催化剂,25℃下,以四氢呋喃为溶剂,可使氯苯与对甲基溴苯的格氏试剂形成4-甲基联苯,具体例子为:
在氮气保护下,在Schlenk反应管内加入6.4mg(0.5mol%)双核镍化合物1,氯苯(112mg,1.0mmol),对甲基溴苯的格氏试剂1.2mmol,25℃反应10小时,加入稀盐酸溶液10mL,后加入乙酸乙酯萃取,有机层用MgSO4干燥,过滤,浓缩,硅胶柱层析分离,得到产物4-甲基联苯,产率:164mg(98%)。1H NMR(400MHz,CDCl3):δ7.58(d,J=8.0Hz,2H),7.51(d,J=8.0Hz,2H),7.44(t,J=7.6Hz,2H),7.32(t,J=7.6Hz,2H),7.24(t,J=7.6Hz,2H),2.38(s,3H)ppm。
实施例2
50℃下,在Schlenk反应管内加入1,2,3-三唑功能化氮杂环卡宾配体L2(527mg,1mmol),氧化银(116mg,0.5mmol)和乙腈20mL,反应15小时,随后加入NiCl2(PPh3)2(654mg,1mmol),在25℃下搅拌反应7小时,离心过滤掉沉淀物,滤液浓缩至2mL,加入20mL无水乙醚,析出固体,过滤收集固体,30℃下真空干燥10h,得到分子结构式为2的1,2,3-三唑功能化氮杂环卡宾双核镍化合物714mg,产率52%。1H NMR(400MHz,d6-DMSO):δ8.79(b,1H),8.46-8.44(m,1H),8.39(s,1H),8.29(t,J=8.0Hz,1H),8.18-8.16(m,1H),8.06(d,J=8.0Hz,1H),7.78-7.72(m,3H),7.37-7.30(m,6H),5.98(s,2H),5.68(s,2H),5.63(s,2H)ppm.13C NMR(400MHz,d6-DMSO):δ157.9(Ni-C),153.9,149.9,147.6,143.1,141.1,140.5,136.2,131.7,130.1,129.3,128.8,128.5,128.3,127.7,125.7,125.5,117.7,116.4,114.8,53.6,53.4,42.9ppm.
利用上述步骤得到的分子结构式为2的1,2,3-三唑功能化氮杂环卡宾双核镍化合物为催化剂,25℃下,以四氢呋喃为溶剂,可使对甲氧基氯苯与对甲基溴苯的格氏试剂形成4-甲氧基-4’-甲基联苯,具体例子为:
在氮气保护下,在Schlenk反应管内加入6.4mg(0.5mol%)双核镍化合物1,对氧基氯苯(142mg,1.0mmol),对甲基溴苯的格氏试剂1.2mmol,25℃反应5小时,加入稀盐酸溶液10mL,后加入乙酸乙酯萃取,有机层用MgSO4干燥,过滤,浓缩,硅胶柱层析分离,得到产物4-甲氧基-4’-甲基联苯,产率:188mg(95%)。1H NMR(400MHz,CDCl3):δ7.53(d,J=8.4Hz,2H),7.47(d,J=8.0Hz,2H),7.24(m,2H),6.97(d,J=8.8Hz,2H),3.85(s,3H),2.38(s,3H)ppm。
实施例3
50℃下,在Schlenk反应管内加入1,2,3-三唑功能化氮杂环卡宾配体L3(443mg,1mmol),氧化银(116mg,0.5mmol)和乙腈20mL,反应15小时,随后加入NiCl2(PPh3)2(654mg,1mmol),在25℃下搅拌反应8小时,离心过滤掉沉淀物,滤液浓缩至2mL,加入20mL无水乙醚,析出固体,过滤收集固体,30℃下真空干燥10h,得到分子结构式为3的1,2,3-三唑功能化氮杂环卡宾双核镍化合物747mg,产率62%。1H NMR(400MHz,DMSO-d6):δ9.05(s,1H,triazole),8.63(d,1H),8.16-8.14(m,2H),7.87(s,1H),7.82(s,1H),7.61-7.58(m,1H),5.68(s,2H),5.65(s,2H),4.18(t,J=7.8Hz,2H),1.79-1.74(m,2H),1.31-1.24(m,2H),0.90(t,3H,J=7.2Hz,).13C NMR(100MHz,DMSO-d6):δ154.2(Ni-C),149.5,148.7,142.0,136.8,125.1,123.2,123.1,122.5,114.2,53.6,49.2,44.0,31.7,19.2,13.7.
利用上述步骤得到的分子结构式为3的1,2,3-三唑功能化氮杂环卡宾双核镍化合物为催化剂,25℃下,以四氢呋喃为溶剂,可使对2-氯吡啶与对甲基溴苯的格氏试剂形成4-甲基-2’-苯基吡啶,具体例子为:
在氮气保护下,在Schlenk反应管内加入6.1mg(0.5mol%)双核镍化合物3,2-氯吡啶(113mg,1.0mmol),对甲基溴苯的格氏试剂1.2mmol,四氢呋喃2mL,25℃反应5小时,加入稀盐酸溶液10mL,后加入乙酸乙酯萃取,有机层用MgSO4干燥,过滤,浓缩,硅胶柱层析分离,得到产物4-甲基-2’-苯基吡啶,产率:169mg(100%)。1H NMR(400MHz,CDCl3):δ8.68(d,J=4.4Hz,1H),7.91(d,J=8.0Hz,2H),7.68(m,2H),7.29(d,J=8.0Hz,2H),7.16(m,1H),2.38(s,3H)ppm。
实施例4
50℃下,在Schlenk反应管内加入1,2,3-三唑功能化氮杂环卡宾配体L4(384mg,1mmol),氧化银(116mg,0.5mmol)和乙腈20mL,反应12小时,随后加入NiCl2(PPh3)2(654mg,1mmol),在25℃下搅拌反应9小时,离心过滤掉沉淀物,滤液浓缩至2mL,加入20mL无水乙醚,析出固体,过滤收集固体,30℃下真空干燥10h,得到分子结构式为4的1,2,3-三唑功能化氮杂环卡宾双核镍化合物588mg,产率57%。1H NMR(400MHz,d6-DMSO):δ8.56(b,1H),8.33(s,1H),7.85(t,J=7.2Hz,1H),7.78(s,2H),7.49(d,J=7.6Hz,1H),7.38-7.32(m,6H),5.65(s,2H),5.66(s,4H)ppm.13C NMR(400MHz,d6-DMSO):δ156.6(Ni-C),153.9,150.1,141.2,138.0,137.5,136.2,129.3,128.8,125.1,124.2,123.9,123.1,123.0,53.6,53.5,44.2ppm.
利用上述步骤得到的分子结构式为4的1,2,3-三唑功能化氮杂环卡宾双核镍化合物为催化剂,80℃下,以甲苯为溶剂,可使对氯甲苯与苯硼酸反应形成4-甲基联苯,具体例子为:
在氮气保护下,在Schlenk反应管内加入2.1mg(0.2mol%)双核镍化合物4,对氯甲苯(126mg,1.0mmol),苯硼酸(145mg,1.2mmol),K3PO4(422mg,2mmol),3mL甲苯,80℃反应3小时,加入水10mL,后加入乙酸乙酯萃取,有机层用MgSO4干燥,过滤,浓缩,硅胶柱层析分离,得到产物4-甲基联苯,产率:164mg(98%)。1H NMR(400MHz,CDCl3):δ7.58(d,J=8.0Hz,2H),7.51(d,J=8.0Hz,2H),7.44(t,J=7.6Hz,2H),7.32(t,J=7.6Hz,2H),7.24(t,J=7.6Hz,2H),2.38(s,3H)ppm。
实施例5
50℃下,在Schlenk反应管内加入1,2,3-三唑功能化氮杂环卡宾配体L5(513mg,1mmol),氧化银(116mg,0.5mmol)和乙腈20mL,反应15小时,随后加入NiCl2(PPh3)2(654mg,1mmol),在25℃下搅拌反应10小时,离心过滤掉沉淀物,滤液浓缩至2mL,加入20mL无水乙醚,析出固体,过滤收集固体,30℃下真空干燥10h,得到分子结构式为5的1,2,3-三唑功能化氮杂环卡宾双核镍化合物713mg,产率53%。1H NMR(400MHz,d6-DMSO):δ9.56(d,J=5.2Hz,1H),9.23(s,1H),8.33(t,J=7.2Hz,1H),8.08-8.04(m,3H),7.91(d,J=7.2Hz,2H),7.76(t,J=6.4Hz,1H),7.71-7.63(m,3H),7.58-7.56(m,2H),6.07(s,2H),5.89(s,2H)ppm.13C NMR(400MHz,d6-DMSO):δ160.5(Ni-C),152.6,141.9,136.9,130.5,129.6,124.4,123.7,122.9,120.7,120.0,124.2,53.6,44.2ppm.
利用上述步骤得到的分子结构式为5的1,2,3-三唑功能化氮杂环卡宾双核镍化合物为催化剂,80℃下,以甲苯为溶剂,可使对氯苯甲醚与苯硼酸形成4-甲氧基联苯,具体例子为:
在氮气保护下,在Schlenk反应管内加入2.6mg(0.2mol%)双核镍化合物5,对氯苯甲醚(142mg,1.0mmol),苯硼酸(145mg,1.2mmol),K3PO4(422mg,2mmol),3mL甲苯,80℃反应5小时,加入水10mL,后加入乙酸乙酯萃取,有机层用MgSO4干燥,过滤,浓缩,硅胶柱层析分离,得到产物4-甲基联苯,产率:164mg(98%)。1H NMR(400MHz,CDCl3):δ7.55(d,J=8.4Hz,2H),7.48(d,J=8.0Hz,2H),7.26(m,2H),6.98(d,J=8.8Hz,2H),3.85(s,3H)ppm。
Claims (2)
1.一种1,2,3-三唑功能化氮杂环卡宾双核镍化合物,其特征在于:所述1,2,3-三唑功能化氮杂环卡宾双核镍化合物的分子结构式I为:
其中R1为咪唑或苯并咪唑,R2为苄基或正丁基或苯基中的一种;
X为PF6或BF4中的一种。
2.一种1,2,3-三唑功能化氮杂环卡宾双核镍化合物的制备方法,其特征在于:将1,2,3-三唑功能化氮杂环卡宾配体和氧化银以2:1的摩尔比加入到盛有1,2,3-三唑功能化氮杂环卡宾配体质量50倍乙腈的Schlenk反应管内,其中所述1,2,3-三唑功能化氮杂环卡宾配体的分子结构式II为:
其中,R1为咪唑或苯并咪唑;
R2为苄基或正丁基或苯基中的一种;
X为PF6或BF4中的一种;
空气氛围中,50℃下,避光搅拌反应10-15小时;随后,加入与1,2,3-三唑功能化氮杂环卡宾配体摩尔比为1:1的NiCl2(PPh3)2,在25℃下搅拌反应5-10小时;离心过滤掉沉淀物,浓缩滤液,加入浓缩液10倍体积的无水乙醚,析出固体,过滤收集固体,30℃下真空干燥10小时,得到分子结构式为I
的1,2,3-三唑功能化氮杂环卡宾双核镍化合物;
其中,R1为咪唑或苯并咪唑;
R2为苄基或正丁基或苯基中的一种;
X为PF6或BF4中的一种。
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