CN107312034A - 基于二亚胺配体的稀土金属配合物及其应用 - Google Patents
基于二亚胺配体的稀土金属配合物及其应用 Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 26
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 23
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910000071 diazene Inorganic materials 0.000 title claims abstract description 15
- 239000003446 ligand Substances 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 238000007281 aminoalkylation reaction Methods 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052706 scandium Inorganic materials 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 6
- PSXUKPCAIKETHF-UHFFFAOYSA-N 2-[4-[3-[4-(4,5-dihydro-1h-imidazol-2-yl)phenoxy]propoxy]phenyl]-4,5-dihydro-1h-imidazole Chemical compound C=1C=C(C=2NCCN=2)C=CC=1OCCCOC(C=C1)=CC=C1C1=NCCN1 PSXUKPCAIKETHF-UHFFFAOYSA-N 0.000 claims description 5
- 102100029579 Diphosphoinositol polyphosphate phosphohydrolase 1 Human genes 0.000 claims description 5
- 150000004982 aromatic amines Chemical class 0.000 claims description 5
- 101710153356 mRNA-decapping protein g5R Proteins 0.000 claims description 5
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 5
- 238000006467 substitution reaction Methods 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 239000003426 co-catalyst Substances 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
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- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 125000001485 cycloalkadienyl group Chemical group 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- -1 aromatic amine hydrogen Chemical class 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract 1
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
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- 125000004836 hexamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
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- 238000002156 mixing Methods 0.000 description 1
- CWOMTHDOJCARBY-UHFFFAOYSA-N n,n,3-trimethylaniline Chemical compound CN(C)C1=CC=CC(C)=C1 CWOMTHDOJCARBY-UHFFFAOYSA-N 0.000 description 1
- AJUXDFHPVZQOGF-UHFFFAOYSA-N n,n-dimethyl-1-naphthylamine Chemical class C1=CC=C2C(N(C)C)=CC=CC2=C1 AJUXDFHPVZQOGF-UHFFFAOYSA-N 0.000 description 1
- KAHVZNKZQFSBFW-UHFFFAOYSA-N n-methyl-n-trimethylsilylmethanamine Chemical compound CN(C)[Si](C)(C)C KAHVZNKZQFSBFW-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229930015698 phenylpropene Natural products 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
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- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- HYWCXWRMUZYRPH-UHFFFAOYSA-N trimethyl(prop-2-enyl)silane Chemical compound C[Si](C)(C)CC=C HYWCXWRMUZYRPH-UHFFFAOYSA-N 0.000 description 1
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- C07F9/02—Phosphorus compounds
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- C07F9/5045—Complexes or chelates of phosphines with metallic compounds or metals
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
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Abstract
本发明属于有机合成的技术领域。本发明的催化剂是基于二亚胺配体的稀土金属配合物。本发明还提供了该稀土金属催化剂在芳香胺氢胺烷基化反应中的应用。
Description
技术领域
本发明属于化学技术领域，具体涉及一种催化剂的用途,尤其涉及稀土金属催化剂在芳香胺氢胺烷基化反应中的应用。
背景技术
芳香胺类化合物广泛存在于天然产物、药物、以及精细化学品中，是一类非常重要的化合物。通过简单芳香胺与烯烃发生氢胺烷基化反应可以高效的构建结构复杂的芳香胺类化合物，由于这是一类100％原子经济性的反应，所以受到人们的极大关注。目前这类反应主要采用第IV、V副族催化剂，且底物必须为伯胺或仲胺，且无法催化三级芳香胺的反应。
发明内容
本发明所要解决的技术问题是利用第III副族的稀土催化剂，高效催化了三级芳香胺的氢胺烷基化反应。
为了解决上述技术问题，本发明提供的技术方案为一种稀土催化剂：基于二亚胺配体的稀土金属配合物，其结构如式所示I：
上述结构式中，RE为Sc，Y及镧系金属，R1为C1-C4烷基，R2为氢或C1-C6烷基或(C1-C4烷基、C3-C6环烷基、芳基)取代的三价磷基，R3为C1-C6烷基，n为1-3，R4为与稀土成键的C1-C6烷基或[三(C1-C10烷基)]硅基取代的C1-C6烷基，表示共轭结构。
本发明优选的技术方案中，二亚胺配体的稀土金属配合物为基于二亚胺配体的稀土金属钪配合物L1，其结构式为式II
其中DIPP代表2,6-二异丙基苯基，表示配位键。
本发明式I的制备方法，包括如下步骤:
第一步：
在有机溶剂中和0℃-110℃下，由结构式为的β二酮与芳胺和芳胺在酸的催化作用下发生脱水缩合反应制得上述配体。或
在有机溶剂中和-78℃-110℃下，由结构式为的亚胺与结构为的亚胺锂盐反应制得上述配体。
第二步：
在有机溶剂中和-78℃-110℃下，由上述制得的配体与RE(R4)3反应生成稀土金属配合物(I)，其中，R1为C1-C4烷基，R2为氢或C1-C6烷基或(C1-C4烷基、C3-C6环烷基、芳基)取代的三价磷基，R3为C1-C6烷基，n为1-3，R4为与稀土成键的C1-C6烷基或[三(C1-C10烷基)]硅基取代的C1-C6烷基，表示共轭结构。
本发明的基于二亚胺配体的稀土金属钪配合物L1式II的制备方法，包括如下步骤:
第一步：
0℃下，向结构为的亚胺锂盐的四氢呋喃溶液中滴加结构为的亚胺的四氢呋喃溶液，滴加完毕，30℃恒温搅拌过夜。反应完成后，抽干四氢呋喃，沉淀物依次用甲苯、己烷萃取，离心，收集上清液。上清液经抽干，己烷洗涤3次，抽干得浅黄色固体。
第二步：
将上述所得固体的甲苯溶液加入到Sc(CH2SiMe3)3(THF)2中，60℃反应4小时。反应完成后，抽干甲苯，己烷洗涤3次，抽干得黄色固体式II化合物，其中DIPP代表2,6-二异丙基苯基，表示配位键。
本发明第二方面提供结构式I的稀土催化剂的用途，用于催化如下的三级芳香胺与烯烃的氢胺烷基化反应，
上述反应中，R5为C1-C4烷基，R6为C1-C4烷基，R7为C1-C4烷基或C1-C4烷氧基或芳基或卤素F、Cl、Br、I，R8为氢或C1-C20烷基或C3-C10环烷基或芳基，R9为氢或C1-C20烷基或含烯基、炔基、烷氧基的C1-C20烷基或C3-C10环烷基或芳基或[三(C1-C10烷基)]硅基，R10为C1-C10烷基或C1-C10烷氧基或[三(C1-C10烷基)]硅基，R11为C1-C4烷基，为乙烯基或环烯基或环二烯基，n1为1-4，n2为1-4，n3为1-2，n4为1-4。
本发明优选的技术方案中，二亚胺配体的稀土金属配合物为基于二亚胺配体的稀土金属钪配合物L1，其结构式为式II：
其中DIPP代表2,6-二异丙基苯基，表示配位键。
本发明优选的技术方案中，共催化剂为[PhNHMe2][B(C6F5)4]、[Ph3C][B(C6F5)4]或者B(C6F5)3。
本发明优选的技术方案中，所述稀土催化剂和共催化剂加入量分别为总反应物的10％mol。
本发明利用第III副族的稀土催化剂，首次实现了三级芳香胺与烯烃的氢胺烷基化反应，反应具有优异的化学选择性与区域选择性，且底物适用范围广。
具体实施方式
以下结合具体实施例对上述方案做进一步说明。应理解，这些实施例是用于说明本发明而不限于限制本发明的范围。实施例中采用的实施条件可以根据具体厂家的条件做进一步调整，未注明的实施条件通常为常规实验中的条件。
介绍和概述
本发明通过举例而非给出限制的方式来进行说明。应注意的是，在本公开文件中所述的“一”或“一种”实施方式未必是指同一种具体实施方式，而是指至少有一种。
下文将描述本发明的各个方面。然而，对于本领域中的技术人员显而易见的是，可根据本发明的仅一些或所有方面来实施本发明。为说明起见，本文给出具体的编号、材料和配置，以使人们能够透彻地理解本发明。然而，对于本领域中的技术人员将显而易见的是，本发明无需具体的细节即可实施。在其他例子中，为不使本发明费解而省略或简化了众所周知的特征。
将各种操作作为多个分立的步骤而依次进行描述，且以最有助于理解本发明的方式来说明；然而，不应将按次序的描述理解为暗示这些操作必然依赖于顺序。
将根据典型种类的反应物来说明各种实施方式。对于本领域中的技术人员将显而易见的是，本发明可使用任意数量的不同种类的反应物来实施，而不只是那些为说明目的而在这里给出的反应物。此外，也将显而易见的是，本发明并不局限于任何特定的混合示例。
实施例1：
称取L1(35mg)，[PhNHMe2][B(C6F5)4](38mg)，溶于甲苯中，室温反应8小时。反应完成，加入N,N-二甲基苯胺(86mg)及1-己烯(40mg)，120℃加热10小时。反应完成后，抽干甲苯得油状残渣，经柱色谱分离得浅黄色油状液体(89mg,91％yield)。
HRMS(ESI)m/z计算值:For C14H23N[M+H]+:206.1903；实测值:206.1909.
1H NMR(400MHz,C6D6,298K):δ＝7.26(m,2H,m-Ph),6.78(m,1H,p-Ph),6.68(m,2H,o-Ph),3.00(dd,2JHH＝14.5Hz,3JHH＝6.6Hz,1H,CH2N),2.80(dd,2JHH＝14.5Hz,3JHH＝8.1Hz,1H,CH2N),2.63(s,3H,CH3N),1.78(m,1H,CHCH3),1.23(m,1H,CHCH2),1.23(m,1H,CH2),1.23(m,2H,CH2CH3),1.10(m,1H,CH2),0.93(m,1H,CHCH2),0.87(t,3JHH＝6.9Hz,3H,CH2CH3),0.77(d,3JHH＝6.7Hz,3H,CHCH3).
13C{1H}NMR(101MHz,C6D6,298K):δ＝150.2(i-Ph),129.5(m-Ph),116.5(p-Ph),112.6(o-Ph),60.0(CH2N),39.3(CH3N),34.7(CHCH2),32.5(CHCH3),29.6(CH2),23.4(CH2CH3),17.9(CHCH3),14.3(CH2CH3)。
实施例2：
称取L1(35mg)，[PhNHMe2][B(C6F5)4](38mg)，溶于甲苯中，室温反应8小时。反应完成，加入N,N-二甲基苯胺(86mg)及1-癸烯(67mg)，120℃加热22小时。反应完成后，抽干甲苯得油状残渣，经柱色谱分离得浅黄色油状液体(100mg,80％yield)。
HRMS(ESI)m/z计算值:For C18H31N[M+H]+:262.2529；实测值:262.2536.
1H NMR(400MHz,C6D6,298K):δ＝7.26(m,2H,m-Ph),6.78(m,1H,p-Ph),6.69(m,2H,o-Ph),3.02(dd,2JHH＝14.5Hz,3JHH＝6.7Hz,1H,CH2N),2.82(dd,2JHH＝14.5Hz,3JHH＝8.0Hz,1H,CH2N),2.64(s,3H,CH3N),1.82(m,1H,CHCH3),1.27(m,13H,CH2),0.99(m,1H,CHCH2),0.92(t,3JHH＝6.8Hz,3H,CH2CH3),0.79(d,3JHH＝6.7Hz,3H,CHCH3).
13C{1H}NMR(101MHz,C6D6,298K):δ＝150.2(i-Ph),129.5(m-Ph),116.5(p-Ph),112.6(o-Ph),60.0(CH2N),39.4(CH3N),35.0(CHCH2),32.5(CHCH3),32.4(CH2),30.5(CH2),30.1(CH2),29.8(CH2),27.5(CH2),23.1(CH2CH3),17.9(CHCH3),14.4(CH2CH3)。
实施例3：
称取L1(35mg)，[PhNHMe2][B(C6F5)4](38mg)，溶于甲苯中，室温反应8小时。反应完成，加入N,N-二甲基苯胺(86mg)及烯丙基三甲基硅烷(54mg)，120℃加热8小时。反应完成后，抽干甲苯得油状残渣，经柱色谱分离得浅黄色油状液体(101mg,90％yield)。
HRMS(ESI)m/z计算值:For C14H25NSi[M+H]+:236.1829；实测值:236.1837.
1H NMR(400MHz,C6D6,298K):δ＝7.26(m,2H,m-Ph),6.78(m,1H,p-Ph),6.70(m,2H,o-Ph),3.00(dd,2JHH＝14.3Hz,3JHH＝6.3Hz,1H,CH2N),2.80(dd,2JHH＝14.3Hz,3JHH＝8.5Hz,1H,CH2N),2.64(s,3H,CH3N),1.98(m,1H,CHCH3),0.83(d,3JHH＝6.6Hz,3H,CHCH3),0.56(dd,2JHH＝14.6Hz,4JHH＝4.0Hz,1H,CH2SiMe3),0.21(dd,2JHH＝14.6Hz,4JHH＝9.8Hz,1H,CH2SiMe3),-0.01(s,9H,SiMe3).
13C{1H}NMR(101MHz,C6D6,298K):δ＝150.3(i-Ph),129.5(m-Ph),116.6(p-Ph),112.6(o-Ph),62.9(CH2N),39.2(CH3N),29.2(CHCH3),22.4(CH2SiMe3),20.8(CHCH3),-0.5(SiMe3)。
实施例4：
称取L1(35mg)，[PhNHMe2][B(C6F5)4](38mg)，溶于甲苯中，室温反应8小时。反应完成，加入N,N-二甲基苯胺(86mg)及4-甲基-1-戊烯(40mg)，120℃加热24小时。反应完成后，抽干甲苯得油状残渣，经柱色谱分离得浅黄色油状液体(68mg,70％yield)。
HRMS(ESI)m/z计算值:For C14H23N[M+H]+:206.1903；实测值:206.1913.
1H NMR(400MHz,C6D6,298K):δ＝7.26(m,2H,m-Ph),6.78(m,1H,p-Ph),6.69(m,2H,o-Ph),3.00(dd,2JHH＝14.4Hz,3JHH＝6.3Hz,1H,CH2N),2.76(dd,2JHH＝14.5Hz,3JHH＝8.3Hz,1H,CH2N),2.62(s,3H,CH3N),1.89(m,1H,CHCH3),1.54(m,1H,CHMe2),1.06(ddd,2JHH＝13.7Hz,3JHH＝8.9Hz,3JHH＝4.9Hz,1H,CHCH2),0.90(m,1H,CHCH2,overlapped with CHCH3),0.86(d,3JHH＝6.6Hz,3H,CHCH3),0.76(t,3JHH＝6.4Hz,6H,CHMe2).
13C{1H}NMR(101MHz,C6D6,298K):δ＝150.3(i-Ph),129.5(m-Ph),116.5(p-Ph),112.6(o-Ph),60.3(CH2N),44.5(CHCH2),39.3(CH3N),30.1(CHCH3),25.5(CHMe2),23.9(CHCH3),22.1,18.0(CHMe2)。
实施例5：
称取L1(35mg)，[PhNHMe2][B(C6F5)4](38mg)，溶于甲苯中，室温反应8小时。反应完成，加入N,N-二甲基-间甲基苯胺(96mg)及1-辛烯(53mg)，120℃加热22小时。反应完成后，抽干甲苯得油状残渣，经柱色谱分离得浅黄色油状液体(96mg,82％yield).
HRMS(ESI)m/z计算值:For C17H29N[M+H]+:248.2373；实测值:248.2384.
1H NMR(400MHz,C6D6,298K):7.21(m,1H,m-Ph),6.63(m,1H,p-Ph),6.58(m,2H,o-Ph),3.06(dd,2JHH＝14.4Hz,3JHH＝6.6Hz,1H,CH2N),2.85(dd,2JHH＝14.4Hz,3JHH＝8.1Hz,1H,CH2N),2.67(s,3H,CH3N),2.28(s,3H,PhCH3),1.85(m,1H,CHCH3),1.25(m,1H,CHCH2),1.25(m,6H,CH2),1.25(m,2H,CH2CH3),0.98(m,1H,CHCH2),0.91(t,3JHH＝6.9Hz,3H,CH2CH3),0.81(d,3JHH＝6.7Hz,3H,CHCH3).
13C{1H}NMR(101MHz,C6D6,298K):δ＝150.4(i-Ph),138.6(m-Ph),129.4(m-Ph),117.5(p-Ph),113.4(o-Ph),110.1(o-Ph),60.0(CH2N),39.5(CH3N),35.0(CHCH2),32.5(CHCH3),32.3(CH2),30.1(CH2),27.4(CH2),23.1(CH2CH3),22.2(PhCH3),17.9(CHCH3),14.4(CH2CH3)。
实施例6：
称取L1(35mg)，[PhNHMe2][B(C6F5)4](38mg)，溶于甲苯中，室温反应8小时。反应完成，加入N,N,3,5-四甲基苯胺(106mg)及1-辛烯(53mg)，120℃加热23小时。反应完成后，抽干甲苯得油状残渣，经柱色谱分离得浅黄色油状液体(96mg,78％yield).
HRMS(ESI)m/z计算值:For C18H31N[M+H]+:262.2529；实测值:262.2525.
1H NMR(400MHz,C6D6,298K):δ＝6.46(m,3H,o,p-Ph),3.10(dd,2JHH＝14.4Hz,3JHH＝6.6Hz,1H,CH2N),2.88(dd,2JHH＝14.4Hz,3JHH＝8.1Hz,1H,CH2N),2.71(s,3H,CH3N),2.29(s,6H,PhCH3),1.88(m,1H,CHCH3),1.27(m,1H,CHCH2),1.27(m,6H,CH2),1.27(m,1H,CH2CH3),1.00(m,1H,CHCH2),0.91(t,3JHH＝6.9Hz,3H,CH2CH3),0.84(d,3JHH＝6.7Hz,3H,CHCH3).
13C{1H}NMR(101MHz,C6D6,298K):δ＝150.5(i-Ph),138.5(m-Ph),118.8(p-Ph),110.9(o-Ph),60.1(CH2N),39.6(CH3N),35.0(CHCH2),32.5(CHCH3),32.3(CH2),30.1(CH2),27.4(CH2),23.1(CH2CH3),22.1(PhCH3),18.0(CHCH3),14.4(CH2CH3)。
实施例7：
称取L1(35mg)，[PhNHMe2][B(C6F5)4](38mg)，溶于甲苯中，室温反应8小时。反应完成，加入5-(N,N-二甲胺基)-茚旦(115mg)及1-辛烯(53mg)，120℃加热23小时。反应完成后，抽干甲苯得油状残渣，经柱色谱分离得浅黄色油状液体(94mg,73％yield)。
HRMS(ESI)m/z计算值:For C19H31N[M+H]+:274.2529；实测值:274.2529.
1H NMR(400MHz,C6D6,298K):δ＝7.17(m,1H,5-C9H9,overlapped with solvent),6.72(m,1H,2-C9H9),6.63(m,1H,6-C9H9),3.07(dd,2JHH＝14.3Hz,3JHH＝6.7Hz,1H,CH2N),2.88(dd,2JHH＝14.6Hz,3JHH＝8.3Hz,1H,CH2N),2.82(dd,2JHH＝16.2Hz,3JHH＝7.7Hz,4H,7-C9H9,9-C9H9),2.71(s,3H,CH3N),1.92(m,2H,8-C9H9),1.92(m,1H,CHCH3),1.27(m,1H,CHCH2),1.27(m,6H,CH2),1.27(m,2H,CH2CH3),1.00(m,1H,CHCH2),0.90(t,3JHH＝6.9Hz,3H,CH2CH3),0.84(d,3JHH＝6.7Hz,3H,CHCH3).
13C{1H}NMR(101MHz,C6D6,298K):δ＝149.7(1-C9H9),145.2(3-C9H9),131.9(4-C9H9),125.0(5-C9H9),111.6(6-C9H9),109.2(2-C9H9),60.7(CH2N),39.9(CH3N),35.1(CHCH2),33.9(7-C9H9),32.5(CHCH3),32.4(9-C9H9),32.3(CH2),30.1(CH2),27.5(CH2),26.3(8-C9H9),23.1(CH2CH3),18.0(CHCH3),14.4(CH2CH3)。
实施例8：
称取L1(35mg)，[PhNHMe2][B(C6F5)4](38mg)，溶于甲苯中，室温反应8小时。反应完成，加入N,N-二甲基苯胺(86mg)及烯丙基苯(56mg)，120℃加热8小时。反应完成后，抽干甲苯得油状残渣，经柱色谱分离得浅黄色油状液体(89mg,78％yield)。
HRMS(ESI)m/z计算值:For C17H21N[M+H]+:240.1747；实测值:240.1760.
1H NMR(400MHz,C6D6,298K):δ＝7.25(m,2H,m-PhN),7.14(m,2H,m-Ph),7.07(m,1H,p-Ph),6.98(m,2H,o-Ph),6.79(m,1H,p-PhN),6.63(m,2H,o-PhN),3.02(dd,2JHH＝14.5Hz,3JHH＝6.1Hz,1H,CH2N),2.79(dd,2JHH＝14.5Hz,3JHH＝7.6Hz,1H,CH2N),2.58(s,3H,CH3N),2.54(m,1H,PhCH2),2.08(m,1H,PhCH2),2.08(m,1H,CHCH3),0.71(d,3JHH＝6.3Hz,3H,CHCH3).
13C{1H}NMR(101MHz,C6D6,298K):δ＝150.1(i-PhN),141.1(i-Ph),129.5(m-PhN),129.4(o-Ph),128.6(m-Ph),126.2(p-Ph),116.6(p-PhN),112.6(o-PhN),59.4(CH2N),41.5(PhCH2),39.3(CH3N),34.7(CHCH3),17.7(CHCH3)。
实施例9：
称取L1(35mg)，[PhNHMe2][B(C6F5)4](38mg)，溶于甲苯中，室温反应8小时。反应完成，加入N,N-二甲基苯胺(86mg)及1-烯丙基萘(80mg)，120℃加热48小时。反应完成后，抽干甲苯得油状残渣，经柱色谱分离得浅黄色油状液体(117mg,85％yield)。
HRMS(ESI)m/z计算值:For C21H23N[M+H]+:290.1903；实测值:290.1911.
1H NMR(400MHz,C6D6,298K):δ＝7.87(m,1H,6-C10H7),7.68(m,1H,7-C10H7),7.59(d,3JHH＝8.2Hz,1H,4-C10H7),7.24(m,1H,3-C10H7),7.24(m,1H,5-C10H7),7.24(m,1H,8-C10H7),7.24(m,2H,m-Ph),7.12(m,1H,2-C10H7),6.79(m,1H,p-Ph),6.63(m,2H,o-Ph),3.17(dd,2JHH＝13.3Hz,3JHH＝4.6Hz,1H,CHCH2),3.00(dd,2JHH＝14.5Hz,3JHH＝7.4Hz,1H,CH2N),2.97(dd,2JHH＝14.5Hz,3JHH＝7.2Hz,1H,CH2N),2.62(s,3H,CH3N),2.41(dd,2JHH＝13.3Hz,3JHH＝9.4Hz,1H,CHCH2),2.29(m,1H,CHCH3),0.69(d,3JHH＝6.5Hz,3H,CHCH3).
13C{1H}NMR(101MHz,C6D6,298K):δ＝150.0(i-Ph),137.3(1-C10H7),134.6(10-C10H7),132.6(9-C10H7),129.5(m-Ph),129.2(7-C10H7),127.5(2-C10H7),127.2(4-C10H7),126.0(5-C10H7),125.7(3-C10H7),125.5(8-C10H7),124.4(6-C10H7),116.7(p-Ph),112.8(o-Ph),60.0(CH2N),39.6(CH3N),38.6(CHCH2),33.8(CHCH3),18.0(CHCH3)。
实施例10：
称取L1(35mg)，[PhNHMe2][B(C6F5)4](38mg)，溶于甲苯中，室温反应8小时。反应完成，加入4-二甲氨基联苯(141mg)及1-辛烯(53mg)，120℃加热45小时。反应完成后，抽干甲苯得油状残渣，经柱色谱分离得浅黄色油状液体(99mg,67％yield)。
HRMS(ESI)m/z计算值:For C22H31N[M+H]+:310.2529；实测值:310.2525.
1H NMR(400MHz,C6D6,298K):δ＝7.63(m,2H,o-Ph),7.58(m,2H,m-PhN),7.29(m,2H,m-Ph),7.13(m,1H,p-Ph),6.72(m,2H,o-PhN),3.04(dd,2JHH＝14.5Hz,3JHH＝6.6Hz,1H,CH2N),2.84(dd,2JHH＝14.5Hz,3JHH＝8.1Hz,1H,CH2N),2.66(s,3H,CH3N),1.83(m,1H,CHCH3),1.26(m,1H,CHCH2),1.26((m,6H,CH2),1.26(m,2H,CH2CH3),0.98(m,1H,CHCH2),0.91(t,3JHH＝6.8Hz,3H,CH2CH3),0.81(d,3JHH＝6.7Hz,3H,CHCH3).
13C{1H}NMR(101MHz,C6D6,298K):δ＝149.5(i-PhN),142.1(i-Ph),129.3(p-PhN),129.1
(m-Ph),128.2(m-PhN),126.7(o-Ph),126.2(p-Ph),112.8(o-PhN),59.8(CH2N),39.4(CH3N),35.0(CHCH2),32.5(CHCH3),32.3(CH2),30.1(CH2),27.4(CH2),23.1(CH2CH3),17.9(CHCH3),14.4(CH2CH3)。
实施例11：
称取L1(35mg)，[PhNHMe2][B(C6F5)4](38mg)，溶于甲苯中，室温反应8小时。反应完成，加入N,N-二甲基苯胺(86mg)及乙烯基环己烷(52mg)，120℃加热21小时。反应完成后，抽干甲苯得油状残渣，经柱色谱分离得浅黄色油状液体(100mg,91％yield)。
HRMS(ESI)m/z计算值:For C16H25N[M+H]+:232.2060；实测值:232.2071.
1H NMR(400MHz,C6D6,298K):δ＝7.28(m,2H,m-Ph),6.79(m,1H,p-Ph),6.71(m,2H,o-Ph),3.15(dd,2JHH＝14.5Hz,3JHH＝5.9Hz,1H,CH2N),2.80(dd,2JHH＝14.5Hz,3JHH＝9.0Hz,1H,CH2N),2.63(s,3H,CH3N),1.67(m,1H,CHCH3),1.67(m,3H,C6H11),1.48(m,2H,C6H11),1.13(m,3H,C6H11),1.02(m,1H,C6H11),0.92(m,2H,C6H11),0.74(d,3JHH＝6.9Hz,3H,CHCH3).
13C{1H}NMR(101MHz,C6D6,298K):δ＝150.2(i-Ph),129.5(m-Ph),116.4(p-Ph),112.6(o-Ph),57.4(CH2N),41.0(C6H11),31.3(C6H11),28.6(C6H11),27.3(C6H11),27.1(C6H11),27.0(C6H11),39.4(CH3N),37.2(CHCH3),14.3(CHCH3)。
实施例12：
称取L1(35mg)，[PhNHMe2][B(C6F5)4](38mg)，溶于甲苯中，室温反应8小时。反应完成，加入N,N-二甲基-1-萘胺(122mg)及1-辛烯(53mg)，120℃加热76小时。反应完成后，抽干甲苯得油状残渣，经柱色谱分离得浅黄色油状液体(51mg,38％yield)。
HRMS(ESI)m/z计算值:For C20H29N[M+H]+:284.2373；实测值:284.2384.
1H NMR(400MHz,C6D6,298K):δ＝8.52(m,1H,3-C10H7),7.70(m,1H,2-C10H7),7.47(m,1H,7-C10H7),7.40(m,1H,4-C10H7),7.30(m,1H,6-C10H7),7.30(m,1H,8-C10H7),7.04(m,1H,5-C10H7),2.89(dd,2JHH＝12.3Hz,3JHH＝6.6Hz,1H,CH2N),2.74(dd,2JHH＝12.3Hz,3JHH＝8.0Hz,1H,CH2N),2.64(s,3H,CH3N),1.75(m,1H,CHCH3),1.49(m,1H,CHCH2),1.24(m,2H,CH2CH3),1.24(m,6H,CH2),1.09(m,1H,CHCH2),0.97(d,3JHH＝6.6Hz,3H,CHCH3),0.90(t,3JHH＝6.7Hz,3H,CH2CH3).
13C{1H}NMR(101MHz,C6D6,298K):δ＝151.4(1-C10H7),135.6(10-C10H7),130.8(9-C10H7),128.7(2-C10H7),126.1(6-C10H7),126.0(8-C10H7),125.5(4-C10H7),124.5(3-C10H7),123.8(7-C10H7),116.6(5-C10H7),63.3(CH2N),44.4(CH3N),35.4(CHCH2),32.3(CH2),30.1(CH2),27.3(CH2),31.6(CHCH3),23.1(CH2CH3),18.4(CHCH3),14.4(CH2CH3)。
以上所述具体实施例仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进或替换，这些改进或替换也应当视为本发明的保护范围。
Claims (6)
1.基于二亚胺配体的稀土金属配合物，其特征在于，其结构如式所示I：
上述结构式中，RE为Sc，Y及镧系金属，R1为C1-C4烷基，R2为氢或C1-C6烷基或(C1-C4烷基、C3-C6环烷基、芳基)取代的三价磷基，R3为C1-C6烷基，n为1-3，R4为与稀土成键的C1-C6烷基或[三(C1-C10烷基)]硅基取代的C1-C6烷基，表示共轭结构。
2.根据权利要求1所述的基于二亚胺配体的稀土金属配合物，其特征在于，所述二亚胺配体的稀土金属配合物为基于二亚胺配体的稀土金属钪配合物L1，其结构式为式II：
其中DIPP代表2,6-二异丙基苯基，表示配位键。
3.如权利要求1所述的结构式I的稀土催化剂的用途，用于催化如下的三级芳香胺与烯烃的氢胺烷基化反应,
上述反应中，R5为C1-C4烷基，R6为C1-C4烷基，R7为C1-C4烷基或C1-C4烷氧基或芳基或卤素F、Cl、Br、I，R8为氢或C1-C20烷基或C3-C10环烷基或芳基，R9为氢或C1-C20烷基或含烯基、炔基、烷氧基的C1-C20烷基或C3-C10环烷基或芳基或[三(C1-C10烷基)]硅基，R10为C1-C10烷基或C1-C10烷氧基或[三(C1-C10烷基)]硅基，R11为C1-C4烷基，为乙烯基或环烯基或环二烯基，n1为1-4，n2为1-4，n3为1-2，n4为1-4。
4.根据权利要求3所述的用途，其特征在于，所述二亚胺配体的稀土金属配合物为基于二亚胺配体的稀土金属钪配合物L1，其结构式为式II：
其中DIPP代表2,6-二异丙基苯基，表示配位键。
5.根据权利要求3所述的用途，其特征在于，共催化剂为[PhNHMe2][B(C6F5)4]、[Ph3C][B(C6F5)4]或者B(C6F5)3。
6.根据权利要求3所述的用途，其特征在于，所述稀土催化剂和共催化剂加入量分别为总反应物的10％mol。
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