CN116410126A - 一种配体、钌配合物及其制备方法和在催化炔烃半氢化反应中的应用 - Google Patents
一种配体、钌配合物及其制备方法和在催化炔烃半氢化反应中的应用 Download PDFInfo
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- CN116410126A CN116410126A CN202310132329.2A CN202310132329A CN116410126A CN 116410126 A CN116410126 A CN 116410126A CN 202310132329 A CN202310132329 A CN 202310132329A CN 116410126 A CN116410126 A CN 116410126A
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- ruthenium complex
- ligand
- hydrogen
- reaction
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- 239000003446 ligand Substances 0.000 title claims abstract description 53
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- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 37
- 239000001257 hydrogen Substances 0.000 claims abstract description 37
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- 150000001336 alkenes Chemical class 0.000 claims abstract description 12
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
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- 238000000034 method Methods 0.000 claims description 18
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- 150000002367 halogens Chemical class 0.000 claims description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 7
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims description 4
- QWFHFNGMCPMOCD-UHFFFAOYSA-N 6-bromopyridine-2-carbaldehyde Chemical compound BrC1=CC=CC(C=O)=N1 QWFHFNGMCPMOCD-UHFFFAOYSA-N 0.000 claims description 4
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—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
- 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
- C07D213/60—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 with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/20—Carbonyls
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
- C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
-
- 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
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
- C07F15/0053—Ruthenium compounds without a metal-carbon linkage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
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Abstract
Description
技术领域
本发明涉及一种配体,还涉及该配体合成的钌配合物,还涉及该配体和钌配合物的制备方法以及该钌配合物在催化炔烃半氢化反应中的应用,属于有机合成技术领域。
背景技术
C=C键是有机化合物中最重要的结构单元之一,广泛存在于各种天然产物和药物中,如何开发更高效绿色策略构建烯烃化合物一直以来是有机化学的研究热点之一。烯烃分为末端烯烃和内烯烃,传统的烯烃的合成大多数是通过炔烃的还原,这类反应相对其它结构的还原比较复杂,主要的原因是烯烃可以进一步被还原成烷烃,因此选择性还原炔烃为烯烃避免过度氢化的烷烃的生成正是此反应的关键所在。炔烃的氢化反应大多数是在氢化釜中进行,这对反应设备要求较高,这也不利于大规模的合成。和末端炔烃的还原相比,内炔的还原由于产品存在立体选择性而更加复杂,如何在避免生成过度氢化的烷烃副产物的同时控制烯烃的顺反构型,是此类反应的难点所在。
为了获得(Z)-烯烃,已经开发了许多催化系统,包括经典教科书中最常用的Lindlar催化剂。由于反应存在立体专一性和立体选择性使(E)-烯烃的合成更难实现。Birch还原碱金属/碱土金属在液氨中还原炔烃化合物可选择性的得到(E)-烯烃,但此类反应底物普适性较差。近年来,过渡金属催化加氢和氢转移反应,在催化炔烃半氢化还原烯烃化反应中得到了广泛应用。而常用的氢源包括H2、HCOOH、NH3BH3等具有易燃易爆、腐蚀性、以及价格昂贵等缺点,从而不利于大规模的生产应用。那么传统的合成内烯烃的方法含有明显的不足,因此开放新的制备方法是化学家们研究的热点之一。
醇是重要的工业原料和中间体,在合成化学中具有广泛的应用。醇的化学性质稳定,且可通过木质纤维素酶解等方式大量制备。利用可再生来源的醇作为原料,向其它高附加值化学品的转化受到了广泛的关注。基于醇的氢转移(借氢)反应是一类具有极高原子经济性和步骤经济性的反应类型,不仅能够实现碳-碳键和碳-杂键的高效构筑,而且副产物仅为水,符合绿色化学的发展理念和要求。以醇为氢源,利用炔烃的还原反应构建C=C双键,虽然报道较少,但也成为近年来新的发展趋势。
以乙醇为氢源进行炔烃还原烯烃化的反应有以下报道:
发明内容
本发明的目的是提供一种配体以及该配体与钌金属前体物形成的钌配合物,该配体及钌配合物均为首次报道,经研究发现,本发明钌配合物能够催化以乙醇为氢源的炔烃还原烯烃化反应,能够立体选择性的将炔烃转变为(E)-烯烃,具有反应条件较为温和、底物普适性好、催化立体选择性好、催化产物收率较高、官能团容忍性好等优点。
本发明具体技术方案如下:
一种配体,其具有下式L所示的结构式:
式L中,R1为氢或C1-C4的烷基;R2为氢或C1-C4的烷基;R3为氢、C1-C4的烷基或卤素。
进一步的,式L中,R1可以为氢、甲基、乙基、丙基、异丙基、丁基;R2可以为氢、甲基、乙基、丙基、异丙基、丁基;R3可以为氢、甲基、乙基、丙基、异丙基、丁基、氟、氯、溴、碘。
上述配体与钌金属前体物[Ru(CO)2Cl2]n发生配位反应,可以得到两种钌配合物,记为钌配合物A和钌配合物B。其中,钌配合物A具有下述式Ⅱ所示的结构式:
式Ⅱ中,R1为C1-C4的烷基;R2为C1-C4的烷基;R3为氢或C1-C4的烷基。
进一步的,式Ⅱ中,R1可以为甲基、乙基、丙基、异丙基、丁基;R2可以为甲基、乙基、丙基、异丙基、丁基;R3可以为氢、甲基、乙基、丙基、异丙基、丁基。
钌配合物B具有下述式Ⅲ所示的结构式:
式Ⅲ中,R1为氢;R2为氢;R3为卤素。
进一步的,式Ⅲ中,R3可以为氟、氯、溴、碘,优选为氯或溴。
进一步的,钌配合物B为离子型配合物,存在游离的氯离子。
进一步的,本发明还提供了上述配体L的制备方法,其包括以下步骤:
进一步的,步骤(1)中,对甲苯磺酸为催化剂,对甲苯磺酸、6-溴吡啶-2-甲醛和乙二醇的摩尔比为0.1-0.2:1:3。
进一步的,步骤(1)中,反应溶剂为甲苯,反应温度为105-115℃,反应时间一般为12-13小时。
进一步的,步骤(2)中,中间体b与2-氨基吡啶的摩尔比为1:1.5。
进一步的,步骤(2)中,碱性条件由KOtBu提供,Pd2(dba)3:dppf:KOtBu:2-氨基吡啶的摩尔比为1:2:100:75。
进一步的,步骤(2)中,反应在溶剂中进行,所述溶剂为THF,回流反应时间为12-13h。
进一步的,步骤(3)中,中间体c与对甲苯磺酸的摩尔比为1:1。
进一步的,步骤(3)中,甲苯与水的体积比为1:0.5-1.5。回流反应的时间一般为12-13h。
进一步的,步骤(4)中,以甲醇为溶剂在室温下反应,反应时间为4-5h。
进一步的,本发明还提供了上述钌配合物的制备方法,该钌配合物可以由上述配体L与[Ru(CO)2Cl2]n反应而得,根据配体L中取代基的不同,可以得到钌配合物A和钌配合物B。
进一步的,所述[Ru(CO)2Cl2]n中,n为大于等于2的整数,例如n=2、3、……等。
进一步的,配体L和[Ru(CO)2Cl2]n的摩尔比为1:1,其中[Ru(CO)2Cl2]n的摩尔量以聚合单体的摩尔量(227.83g/mol)计。
进一步的,反应在气体保护、溶剂环境中进行。所述溶剂为甲醇,保护气体为氮气等惰性气体。
进一步的,反应在常温下进行。
本发明还提供了上述钌配合物A和钌配合物B作为催化剂在催化炔烃半氢化还原制备烯烃中的应用。
本发明还提供了一种炔烃半氢化还原制备烯烃的方法,以炔烃为原料,以乙醇为氢源,以上述钌配合物为催化剂,经半氢化还原反应得到(E)-烯烃。
进一步的,炔烃半氢化还原反应在气体保护、碱性环境下进行,所述碱性环境由叔丁醇钠等提供,保护气体为氮气等惰性气体。
本发明首次报道了一种特殊结构的配体以及该配体与钌金属前体物形成的钌配合物,该配体和钌配合物合成步骤简单,该钌配合物在催化以乙醇为氢源的炔烃还原烯烃化反应中能立体选择性的生成(E)-烯烃,具有反应条件较为温和、底物普适性好、催化剂立体选择性好、催化产物收率较高、官能团容忍性好等优点。
附图说明
图1为化合物2a在氘代氯仿中的氢谱。
图2为化合物2a在氘代氯仿中的碳谱。
图3为化合物2b在氘代氯仿中的氢谱。
图4为化合物2b在氘代氯仿中的碳谱。
图5为化合物2c在氘代氯仿中的氢谱。
图6为化合物2c在氘代氯仿中的碳谱。
图7为化合物2f在氘代氯仿中的氢谱。
图8为化合物2f在氘代氯仿中的碳谱。
图9为化合物2l在氘代氯仿中的氢谱。
图10为化合物2l在氘代氯仿中的碳谱。
具体实施方式
以下实施例中,所用的化学试剂均为市售的化学纯或者分析纯。使用标准的Schlenk和真空管线技术,在干燥和纯化的氮气气氛下进行所有操作。在使用前,所有溶剂均在N2氛下适当的干燥剂中进行干燥处理。1H和13C NMR光谱在Zhongke-Niujin Quantum-I400MHz光谱仪上表征。高分辨质谱(HR-MS)使用Agilent 6210ESI-TOF质谱仪。
一、配体的合成及表征
配体的合成流程如下:
实施例1合成配体(E)-6-((2,6-二异丙基苯基)亚氨基)甲基-N-(吡啶-2-基)吡啶-2-胺(L1)
在100mL反应容器中装入6-溴吡啶-2-甲醛(1.86g,10.0mmol),乙二醇(1.86g,30.0mmol),对甲苯磺酸(0.172g,1mmol)和甲苯(40mL)。将混合物在110℃下搅拌12h,反应期间用分水器除水。冷却至室温后,加入15mL饱和碳酸钾水溶液,分液合并有机相。有机相用蒸馏水水洗三次(3×15mL),得到的有机相用无水Na2SO4干燥并过滤,真空除去溶剂后得淡黄色液体,即中间体b(2.061g,收率90%)。按照此步骤可以重复操作,以得到更多的中间体。
氩气环境下,在装有磁子的100ml单口瓶中装入中间体b(1.145g,5.0mmol),2-氨基吡啶(0.72g,7.5mmol),Pd2(dba)3(0.09g,0.1mmol),dppf(0.119g,0.2),KOtBu(1.12g,10mmol)和THF(25mL),混合物加热回流12h。反应后,冷却至室温,过滤,收集有机相。合并的有机相在减压下浓缩,然后将残余物通过硅胶柱色谱纯化(石油醚:乙酸乙酯10∶1,v/v),得到白色固体中间体c(0.972g,收率80%)按照此步骤可以重复操作,以得到更多的中间体。
在100mL反应容器中装入中间体c(1.215g,5mmol),对甲苯磺酸(0.86g,5mmol),甲苯(20mL),蒸馏水(20mL),混合物在110℃下搅拌12h。反应后冷却至室温,加入20mL饱和碳酸钾水溶液,并将所得溶液用二氯甲烷(3×15mL)萃取。合并的有机相用无水Na2SO4干燥并过滤,真空除去溶剂后,将残余物通过硅胶柱色谱法纯化(石油醚:乙酸乙酯10∶1,v/v)),得到白色固体中间体d(64.68mg,收率65%)。
在50ml反应容器中加入中间体d(0.995g,5mmol),2,6-二异丙基苯胺(1.062g,6mmol),1滴甲酸和10ml甲醇,混合物在室温下搅拌4小时,过滤得到固体粗产品。粗产品用冷甲醇洗三次,干燥后得配体L1,为白色固体(1.593g,收率89%)。
配体L1的表征结果如下所示:
1H NMR(400MHz,CDCl3):δ8.29(d,J=4.8Hz,1H),8.21(s,1H),7.75(t,J=5.6Hz,4H),7.59(d,J=3.1Hz,2H),7.20–7.09(m,3H),6.87(m,1H),3.05–2.93(m,2H),1.18(d,J=6.9Hz,12H)ppm.
13C NMR(101MHz,CDCl3)δ:163.06,154.01,152.40,148.86,147.87,138.51,137.95,137.33,124.47,123.15,116.79,114.66,113.63,111.76,28.07,23.60ppm.
MS(ESI,m/z)=359.2[M+H]+.
实施例2合成配体(E)-6-((2,4,6-三甲基苯基)亚氨基)甲基-N-(吡啶-2-基)吡啶-2-胺(L2)
配体L2的合成与配体L1的方法相似,具体为:按照实施例1的方法合成中间体d,在50ml反应容器中加入中间体d(0.995g,5mmol),2,4,6-三甲基苯胺(0.81g,6mmol),1滴甲酸和10ml甲醇,混合物在室温下搅拌4小时,过滤得到固体粗产品。粗产品用冷甲醇冲洗三次,干燥后得配体L2,为白色固体(1.34g,收率85%)。
配体L2的表征结果如下所示:
1H NMR(400MHz,CDCl3):δ8.28(d,J=4.9Hz,1H),8.22(s,1H),7.74(s,4H),7.60(s,2H),6.92–6.85(m,3H),2.29(s,3H),2.14(s,6H)ppm.
13C NMR(101MHz,CDCl3):δ163.49,153.84,152.44,147.92,138.16,133.35,128.79,126.89,116.72,114.43,113.25,111.85,20.80,18.31.
MS(ESI,m/z)=317.2[M+H]+.
实施例3合成配体(E)-6-((4-氯苯基)亚氨基)甲基-N-(吡啶-2-基)吡啶-2-胺(L3)
配体L3的合成与配体L1的方法相似,具体为:在50ml反应容器中加入中间体d(0.995g,5mmol),4-氯苯胺(0.762g,6mmol),1滴甲酸和10ml甲醇,混合物在室温下搅拌4小时,过滤得到固体粗产品。粗产品用冷甲醇冲洗三次,干燥后得配体L3,为白色固体(1.232g,收率80%)。
配体L3的表征结果如下所示:
1H NMR(400MHz,CDCl3)δ:8.49(s,1H),8.32(d,J=4.1Hz,1H),7.90–7.76(m,2H),7.68(s,4H),7.42(d,J=8.4Hz,2H),7.29(d,J=8.1Hz,2H),6.95(s,1H)ppm.
13C NMR(101MHz,CDCl3)δ:161.39,154.26,153.87,152.24,150.68,147.87,138.32,136.78,132.56,122.91,120.07,116.72,115.12,113.95,112.01ppm.
MS(ESI,m/z)=309.1[M+H]+.
实施例4合成配体(E)-6-(((4-溴苯基)亚氨基)甲基)-N-(吡啶-2-基)吡啶-2-胺(L4)
配体L4的合成与配体L1的方法相似,具体为:按照实施例1的方法合成中间体d,在50ml反应容器中加入中间体d(0.995g,5mmol),4-溴苯胺(1.032g,6mmol),1滴甲酸和10ml甲醇,混合物在室温下搅拌4小时,过滤得到固体粗产品。粗产品用冷甲醇洗三次,干燥后得配体L4,为白色固体(1.408g,收率80%)。
配体L4的表征结果如下所示:1H NMR(400MHz,CDCl3):δ8.44(s,1H),8.30(d,J=4.0Hz,1H),7.89(s,1H),7.78–7.47(m,7H),7.15(d,J=8.2Hz,2H),6.89(t,J=5.6Hz,1H)ppm.
13C NMR(101MHz,CDCl3)δ:161.09,154.04,153.81,152.04,150.27,147.76,138.48,137.98,132.28,122.85,120.07,116.72,115.62,113.85,111.91ppm.
MS(ESI,m/z)=353.1[M+H]+.
二、钌配合物的合成与表征
钌配合物的合成流程如下:
实施例5钌配合物1的合成
实验操作都是在氮气气体氛围下使用标准Schlenk技术进行的。[Ru(CO)2Cl2]n(68.34mg,0.3mmol)和配体L1(0.107g,0.3mmol)在甲醇(10mL)中室温搅拌24h。将所得反应混合物减压浓缩,冷冻析出橙红色固体,为钌配合物1(0.117g,收率67%)。
钌配合物1的表征结果如下:
HR-MS(ESI-TOF):calcd for C25H26Cl2N4O2Ru,[M-Cl]+551.0782,found 551.0786.
1H NMR(400MHz,CDCl3)δ:8.88(d,J=8.6Hz,1H),8.45–8.36(m,2H),8.01(t,J=7.7Hz,1H),7.72(t,J=7.5Hz,1H),7.57(d,J=6.9Hz,1H),7.39–7.26(m,4H),7.09–7.02(m,1H),6.96(d,J=8.1Hz,1H),3.60(t,J=13.3,6.6Hz,2H),1.29(d,J=6.6Hz,6H),1.07(d,J=6.8Hz,6H)ppm.
13C NMR(101MHz,CDCl3)δ:195.07,193.59,155.74,152.05,151.72,147.60,146.72,141.45,140.05,138.77,128.59,124.57,122.99,119.59,118.63,26.17,23.15ppm.
实施例6钌配合物2的合成
实验操作都是在氮气气体氛围下使用标准Schlenk技术进行的。[Ru(CO)2Cl2]n(68.34mg,0.3mmol)和配体L2(0.0948g,0.3mmol),在甲醇(10mL)中室温搅拌24h,将反应所得混合物减压浓缩,冷冻析出橙红色固体,为钌配合物2(0.115g,收率71%)。
钌配合物2的表征结果如下:
HR-MS(ESI-TOF):calcd for C22H20Cl2N4O2Ru,[M-Cl]+509.0313,found 509.0318.
1H NMR(400MHz,CDCl3)δ:8.85(d,J=8.8Hz,1H),8.45–8.35(m,2H),8.00(t,J=7.9Hz,1H),7.71(t,J=7.7Hz,1H),7.54(t,J=8.0Hz,1H),7.07–6.89(m,5H),2.41(s,6H),2.33(s,3H)ppm.
13C NMR(101MHz,CDCl3)δ:171.74,155.36,152.34,151.60,147.23,147.02,139.19,137.49,130.29,129.84,123.30,120.14,118.33,112.70,20.83,20.19ppm.
实施例7钌配合物3的合成
实验操作都是在氮气气体氛围下使用标准Schlenk技术进行的。[Ru(CO)2Cl2]n(68.34mg,0.3mmol)和配体L3(0.092g,0.3mmol),在甲醇(10mL)中室温搅拌24h,将反应所得混合物减压浓缩,冷冻析出橙色固体,为钌配合物3(0.117g,收率73%)。
钌配合物3的表征结果如下:
HR-MS(ESI-TOF):calcd for C19H13Cl3N4O2Ru,[M+H]+536.9220,found 536.9218.
1H NMR(400MHz,CDCl3)δ:8.81(d,J=8.7Hz,1H),8.56(s,1H),8.42(d,J=4.1Hz,1H),8.05–7.99(m,1H),7.78(t,J=7.0Hz,1H),7.72–7.56(m,6H),7.13–7.07(m,1H),7.02(d,J=8.1Hz,1H)ppm.
13C NMR(101MHz,CDCl3)δ:194.57,194.10,193.38,167.62,155.80,152.20,151.41,149.34,147.85,139.93,138.67,133.04,123.57,123.40,119.93,118.81,112.65ppm.
实施例8钌配合物4的合成
实验操作都是在氮气气体氛围下使用标准Schlenk技术进行的。[Ru(CO)2Cl2]n(68.34mg,0.3mmol)和配体L4(0.105g,0.3mmol),在甲醇(10mL)中室温搅拌24h,将反应所得混合物减压浓缩,冷冻析出橙色固体,为钌配合物4(0.113g,收率65%)。
钌配合物4的表征结果如下:
HR-MS(ESI-TOF):calcd for C19H13BrCl2N4O2Ru,[M+H]+580.8715,found580.8712.
1H NMR(400MHz,CDCl3)δ:8.73(s,1H),8.61(s,1H),8.39(d,J=33.6Hz,2H),8.10(s,1H),8.03(s,1H),7.88(d,J=20.1Hz,2H),7.68(d,J=6.0Hz,2H),7.42(s,2H),7.01(s,1H)ppm.
13C NMR(101MHz,CDCl3)δ:168.92,164.76,155.45,154.78,150.72,150.59,149.87,149.49,147.67,139.97,133.17,125.57,123.31,121.56,119.73,119.24,116.73ppm.
三、钌配合物用作催化剂催化炔烃的半氢化还原反应生成(E)-烯烃
以实施例5中合成的钌配合物1为例,以乙醇为氢源,研究钌配合物对炔烃的半氢化还原反应的催化性能。
实施例9(E)-烯烃化合物2a,E的合成
在10ml Schlenk(双排管)中加入二苯乙炔1a(89.11mg,0.50mmol),钌配合物1(2.93mg,0.005mmol)和t-BuONa(28.00mg,0.24mmol)。在氮气氛围下,加入2mL的乙醇并在110℃下搅拌10h。反应后冷却至室温,在减压下浓缩,然后将残余物通过快速柱色谱法(石油醚)纯化,得到白色固体(E)-烯烃(记为2a,E)(86.40mg,收率96%)。(E)-烯烃的核磁信息如下:
1H NMR(400MHz,CDCl3)δ:7.50(d,J=7.4Hz,4H),7.34(t,J=7.6Hz,4H),7.24(m,2H),7.10(s,2H)ppm.13C NMR(101MHz,CDCl3)δ:137.41,128.77,127.70,126.60ppm.
此外,反应过程中还生成副产物(Z)-烯烃(记为2a,Z)和过度氢化的烷烃1A。不同构型的二苯乙烯2a,E、2a,Z以及过度氢化的烷烃1A的比例通过核磁内标法鉴定,结果为:2a,E:2a,Z比例大于99:1,过度氢化的烷烃1A含量为1%,最终2a,E分离收率为96%。
实施例10(E)-烯烃化合物2b,E的合成
在10ml Schlenk中加入1-甲基-4-苯乙炔基苯1b(96.05mg,0.50mmol),钌配合物1(2.93mg,0.005mmol)和t-BuONa(28.00mg,0.24mmol)。在氮气氛围下,加入2mL的乙醇并在110℃下搅拌10h。反应后冷却至室温,在减压下浓缩,然后将残余物通过快速柱色谱法(石油醚)纯化,得到白色固体2b,E(94.13mg,收率97%)。2b,E的核磁信息为:1H NMR(400MHz,CDCl3)δ:7.49(d,J=7.6Hz,2H),7.41(d,J=8.0Hz,2H),7.34(t,J=7.6Hz,2H),7.23(m,1H),7.16(d,J=7.9Hz,2H),7.07(d,J=2.3Hz,2H),2.35(s,3H)ppm.13C NMR(101MHz,CDCl3)δ:137.57,134.60,129.45,128.69,128.45,127.75,127.46,126.48,126.45,21.32ppm.
此外,反应过程中还生成副产物(Z)-烯烃(记为2b,Z)和过度氢化的烷烃2A。不同构型的二苯乙烯以及过度氢化的烷烃A的比例2通过核磁内标法鉴定,结果为:2b,E:2b,Z比例大于99:1,过度氢化的烷烃2A含量小于1%,最终2b,E分离收率为97%。
实施例11(E)-烯烃化合物2c,E的合成
在10ml Schlenk中加入1-氯-4-苯乙炔基苯1c(106.0mg,0.50mmol),钌配合物1(2.93mg,0.005mmol)和t-BuONa(28.00mg,0.24mmol)。在氮气氛围下,加入2mL的乙醇并在110℃下搅拌10h。冷却至室温后,在减压下浓缩,然后将残余物通过快速柱色谱法(石油醚)纯化,得到白色固体2c,E(101.6mg,收率95%)。2c,E的核磁信息为:1H NMR(400MHz,CDCl3)δ:7.49(d,J=7.6Hz,2H),7.42(d,J=8.4Hz,2H),7.32(m,5H),7.05(d,J=2.6Hz,2H)ppm.13C NMR(101MHz,CDCl3)δ:137.01,135.88,133.21,129.35,128.88,128.78,127.92,127.70,127.40,126.59ppm.
此外,反应过程中还生成副产物(Z)-烯烃(记为2c,Z)和过度氢化的烷烃3A。不同构型的二苯乙烯以及过度氢化的烷烃3A的比例通过核磁内标法鉴定,结果为:2c,E:2c,Z比例大于99:1,过度氢化的烷烃3A含量小于1%,最终2c,E分离收率为95%。
实施例12(E)-烯烃化合物2d,E的合成
在10ml Schlenk中加入1-溴-4-苯乙炔基苯1d(128.0mg,0.50mmol),钌配合物1(2.93mg,0.005mmol)和t-BuONa(28.00mg,0.24mmol)。在氮气氛围下,加入2mL的乙醇并在110℃下搅拌10h。冷却至室温后,在减压下浓缩,然后将残余物通过快速柱色谱法(石油醚)纯化,得到白色固体2d,E(0.1238g,收率96%)。2d,E的核磁信息为:1H NMR(400MHz,CDCl3)δ:7.60–7.48(m,4H),7.42(d,J=7.9Hz,4H),7.33(m,1H),7.12(q,J=16.3Hz,2H)ppm.13CNMR(101MHz,CDCl3)δ:137.01,136.33,131.84,129.38,128.82,128.05,127.98,127.46,126.64,121.38ppm.
此外,反应过程中还生成副产物(Z)-烯烃(记为2d,Z)和过度氢化的烷烃4A。不同构型的二苯乙烯以及过度氢化的烷烃4A的比例通过核磁内标法鉴定,结果为:2d,E:2d,Z比例大于99:1,过度氢化的烷烃4A含量为1%,最终2d,E分离收率为96%。
实施例13(E)-烯烃化合物2e,E的合成
在10ml Schlenk中加入1-三氟甲基-4-苯乙炔基苯1e(123.0mg,0.50mmol),钌配合物1(2.93mg,0.005mmol)和t-BuONa(28.00mg,0.24mmol)。在氮气氛围下,加入2mL的乙醇并在110℃下搅拌10h。冷却至室温后,在减压下浓缩,然后将残余物通过快速柱色谱法(石油醚)纯化,得到白色固体2e,E(0.119g,收率96%)。2e,E的核磁信息为:1H NMR(400MHz,CDCl3)δ:7.60–7.46(m,6H),7.36(t,J=7.5Hz,2H),7.28(t,J=7.1Hz,1H),7.16(d,J=16.4Hz,1H),7.08(d,J=16.3Hz,1H)ppm.13C NMR(101MHz,CDCl3)δ:140.85,136.68,131.24,128.86,128.36,127.16,126.84,126.63,125.70,125.60ppm.19F NMR(376MHz,CDCl3)δ:
-62.35(s)ppm.
此外,反应过程中还生成副产物(Z)-烯烃(记为2e,Z)和过度氢化的烷烃5A。不同构型的二苯乙烯以及过度氢化的烷烃5A的比例通过核磁内标法鉴定,结果为:2e,E:2e,Z比例大于99:1,过度氢化的烷烃5A含量小于1%,最终2e,E分离收率为96%。
实施例14(E)-烯烃化合物2f,E的合成
在10ml Schlenk中加入1-甲基-3-苯乙炔基苯1f(96.05mg,0.50mmol),钌配合物1(2.93mg,0.005mmol)和t-BuONa(28.00mg,0.24mmol)。在氮气氛围下,加入2mL的乙醇并在110℃下搅拌10h。冷却至室温后,在减压下浓缩,然后将残余物通过快速柱色谱法(石油醚)纯化,得到无色液体2f,E(92.20mg,收率95%)。2f,E的核磁信息为:1H NMR(400MHz,CDCl3)δ:7.49(d,J=7.3Hz,2H),7.32(dd,J=15.6,8.2Hz,4H),7.23(t,J=7.5Hz,2H),7.06(d,J=8.5Hz,3H),2.36(s,3H)ppm.13C NMR(101MHz,CDCl3)δ:138.30,137.52,137.36,128.90,128.77,128.68,128.57,127.64,127.32,126.59,123.82,21.40ppm.
此外,反应过程中还生成副产物(Z)-烯烃(记为2f,Z)和过度氢化的烷烃6A。不同构型的二苯乙烯以及过度氢化的烷烃6A的比例通过核磁内标法鉴定,结果为:2f,E:2f,Z比例大于99:1,过度氢化的烷烃6A含量为1%,最终2f,E分离收率为95%。
实施例15(E)-烯烃化合物2g,E的合成
在10ml Schlenk中加入1-氯-3-苯乙炔基苯1g(106.mg,0.50mmol),钌配合物1(2.93mg,0.005mmol)和t-BuONa(28.00mg,0.24mmol)。在氮气氛围下,加入2mL的乙醇并在110℃下搅拌10h。冷却至室温后,在减压下浓缩,然后将残余物通过快速柱色谱法(石油醚)纯化,得到无色液体2g,E(99.5mg,收率93%)。2g,E的核磁信息为:1H NMR(400MHz,CDCl3)δ:7.49–7.43(m,3H),7.36–7.29(m,3H),7.27–7.16(m,3H),7.08–7.01(m,1H),6.97(d,J=16.3Hz,1H)ppm.13C NMR(101MHz,CDCl3)δ:139.32,136.90,134.73,130.20,129.96,128.86,128.14,127.58,127.28,126.78,126.41,124.86ppm.
此外,反应过程中还生成副产物(Z)-烯烃(记为2g,Z)和过度氢化的烷烃7A。不同构型的二苯乙烯以及过度氢化的烷烃7A的比例通过核磁内标法鉴定,结果为:2g,E:2g,Z比例大于99:1,过度氢化的烷烃7A含量为3%,最终2g,E分离收率为93%。
实施例16(E)-烯烃化合物2h,E的合成
在10ml Schlenk中加入1-甲基-2-苯乙炔基苯1h(96.05mg,0.50mmol),钌配合物1(2.93mg,0.005mmol)和t-BuONa(28.00mg,0.24mmol)。在氮气氛围下,加入2mL的乙醇并在110℃下搅拌20h。冷却至室温后,在减压下浓缩,然后将残余物通过快速柱色谱法(石油醚)纯化,得到无色液体2h,E(91.23mg,收率94%)。2h,E的核磁信息为:1H NMR(400MHz,CDCl3)δ:7.57(d,J=7.1Hz,1H),7.50(d,J=7.4Hz,2H),7.33(m,3H),7.25–7.15(m,4H),7.01–6.94(m,1H),2.41(s,3H)ppm.13C NMR(101MHz,CDCl3)δ:137.79,136.51,135.89,130.12,128.80,127.69,126.67,127.68,126.65,126.33,125.48,20.04ppm.
此外,反应过程中还生成副产物(Z)-烯烃(记为2h,Z)和过度氢化的烷烃8A。不同构型的二苯乙烯以及过度氢化的烷烃8A的比例通过核磁内标法鉴定,结果为:2h,E:2h,Z比例大于99:1,过度氢化的烷烃8A含量为2%,最终2h,E分离收率为94%。
实施例17(E)-烯烃化合物2i,E的合成
在10ml Schlenk中加入1-氯-2-苯乙炔基苯1i(106.0mg,0.50mmol),钌配合物1(2.93mg,0.005mmol)和KOtBu(28.00mg,0.25mmol)。在氮气氛围下,加入2mL的乙醇并在110℃下搅拌20h。冷却至室温后,在减压下浓缩,然后将残余物通过快速柱色谱法(石油醚)纯化,得到无色液体2i,E(102.7mg,收率96%)。2i,E的核磁信息为:1H NMR(400MHz,CDCl3)δ:7.76(m,1H),7.63(m,3H),7.46(t,J=7.7Hz,3H),7.40–7.24(m,4H),7.16(d,J=16.3Hz,1H)ppm.13C NMR(101MHz,CDCl3)δ:137.15,135.50,133.54,131.35,129.91,128.83,128.62,128.16,127,126.93,126.56,124.84ppm.
此外,反应过程中还生成副产物(Z)-烯烃(记为2i,Z)和过度氢化的烷烃9A。不同构型的二苯乙烯以及过度氢化的烷烃9A的比例通过核磁内标法鉴定,结果为:2i,E:2i,Z比例大于99:1,过度氢化的烷烃9A含量小于1%,最终2i,E分离收率为96%。
实施例18(E)-烯烃化合物2j,E的合成
在10mlSchlenk中加入2-(苯乙炔基)萘1j(114.0mg,0.50mmol),钌配合物1(2.93mg,0.005mmol)和t-BuONa(28.00mg,0.24mmol)。在氮气氛围下,加入2mL的乙醇并在110℃下搅拌10h。冷却至室温后,在减压下浓缩,然后将残余物通过快速柱色谱法(石油醚)纯化,得到白色固体2j,E(111.6mg,收率97%)。2j,E的核磁信息为:1H NMR(400MHz,CDCl3)δ:7.85-7.77(m,4H),7.73(m,1H),7.55(d,J=7.4Hz,2H),7.49–7.40(m,2H),7.37(t,J=7.5Hz,2H),7.30–7.21(m,3H)ppm.13C NMR(101MHz,CDCl3)δ:137.41,134.87,133.76,133.10,129.08,129.08,128.59,128.37,128.06,127.75,126.70,126.61,126.40,125.96,123.56ppm.
此外,反应过程中还生成副产物(Z)-烯烃(记为2j,Z)和过度氢化的烷烃10A。不同构型的二苯乙烯以及过度氢化的烷烃10A的比例通过核磁内标法鉴定,结果为:2j,E:2j,Z比例大于99:1,过度氢化的烷烃10A含量小于1%,最终2j,E分离收率为97%。
实施例19(E)-烯烃化合物2k,E的合成
在10ml Schlenk中加入1,2-二-对甲苯炔1k(103.0mg,0.50mmol),钌配合物1(2.93mg,0.005mmol)和t-BuONa(28.00mg,0.24mmol)。在氮气氛围下,加入2mL的乙醇并在110℃下搅拌10h。冷却至室温后,在减压下浓缩,然后将残余物通过快速柱色谱法(石油醚)纯化,得到白色固体2k,E(99.90mg,收率96%)。2k,E的核磁信息为:1H NMR(400MHz,CDCl3)δ:7.38(d,J=7.9Hz,4H),7.12(t,J=10.0Hz,4H),7.02(s,2H),2.32(d,J=9.1Hz,6H)ppm.13CNMR(101MHz,CDCl3)δ:137.33,134.82,129.46,127.71,126.40,21.33ppm.
此外,反应过程中还生成副产物(Z)-烯烃(记为2k,Z)和过度氢化的烷烃11A。不同构型的二苯乙烯以及过度氢化的烷烃11A的比例通过核磁内标法鉴定,结果为:2k,E:2k,Z比例大于99:1,过度氢化的烷烃11A含量小于1%,最终2k,E分离收率为96%。
实施例20(E)-烯烃化合物2L,E的合成
在10ml Schlenk中加入二(4-溴苯基)乙炔1L(167.0mg,0.50mmol),钌配合物1(2.93mg,0.005mmol)和t-BuONa(28.00mg,0.24mmol)。在氮气氛围下,加入2mL的乙醇并在110℃下搅拌10h。冷却至室温后,在乙醇中重结晶得到白色固体2L,E(144.5mg,收率86%)。2L,E的核磁信息为:1H NMR(400MHz,CDCl3)δ:7.48(d,J=8.4Hz,4H),7.36(d,J=8.4Hz,4H),7.01(s,2H)ppm.13C NMR(101MHz,CDCl3)δ:135.93,131.89,128.15,128.04,121.67ppm.
此外,反应过程中还生成副产物(Z)-烯烃(记为2L,Z)和过度氢化的烷烃12A。不同构型的二苯乙烯以及过度氢化的烷烃12A的比例通过核磁内标法鉴定,结果为2L,E:2L,Z比例大于99:1,过度氢化的烷烃12A含量小于1%,最终2L,E分离收率为86%。
实施例21
按照实施例9的方法合成烯烃化合物(E)-2a,不同的是:将钌配合物1分别替换为等摩尔量的钌配合物2、钌配合物3、钌配合物4。结果如下表1所示:
表1
二苯乙烯2a,E、2a,Z以及过度氢化的烷烃1A的比例通过核磁内标法鉴定。
Claims (10)
5.一种权利要求2或3所述的钌配合物的制备方法,其特征是:由权利要求1所述的配体和[Ru(CO)2Cl2]n反应而得。
6.根据权利要求5所述的制备方法,其特征是:配体L和[Ru(CO)2Cl2]n的摩尔比为1:1,其中[Ru(CO)2Cl2]n的摩尔量以聚合单体的摩尔量计。
7.根据权利要求5所述的制备方法,其特征是:反应在气体保护、甲醇溶剂中进行。
8.权利要求2或3所述的钌配合物在催化炔烃半氢化还原制备烯烃中的应用。
10.根据权利要求9所述的方法,其特征是:半氢化还原反应在气体保护、碱性环境下进行,所述碱性由叔丁醇钠提供,保护气体为惰性气体。
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