CN113234104B - 钳形钼配合物及其制备方法、催化组合物和应用及醇制备方法 - Google Patents

钳形钼配合物及其制备方法、催化组合物和应用及醇制备方法 Download PDF

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CN113234104B
CN113234104B CN202110478124.0A CN202110478124A CN113234104B CN 113234104 B CN113234104 B CN 113234104B CN 202110478124 A CN202110478124 A CN 202110478124A CN 113234104 B CN113234104 B CN 113234104B
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王征
张相龙
杜兰星
马宁
韩鹏
李思锦
王鑫
张璇
张晨雨
张思雨
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Hebei Agricultural University
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Abstract

本发明公开了一种钳型钼配合物、制备方法及相应的催化剂组合物和用途，通过2‑(取代基乙基)‑(5,6,7,8‑四氢喹啉基)胺与相应的羰基钼金属前体进行配位反应得到不同结构的9种钼配合物。然后通过钼配合物催化酮类化合物转移氢化反应，生成了40例醇类化合物。本发明中钼配合物的制备方法简单、收率高、稳定性好。对于酮的转移氢化反应，钼基催化体系的催化活性高、钼负载量小，用于芳香族和脂肪族醇的生产，方法简单、环境污染小、收率高。

Description

钳形钼配合物及其制备方法、催化组合物和应用及醇制备 方法
技术领域
本发明涉及一种钳形钼配合物及其制备方法，以及以该配合物为活性成分的催化剂组合物和该催化剂组合物在催化羰基酮类化合物转移氢化成醇的反应中的应用。
背景技术
醇类化合物是制备洗涤剂、表面活性剂、增塑剂等各种精细化学品的基础化工原料，其重要的化学转化方法是将羰基酮类还原成相应的醇，然而与传统的采用化学计量的金属氢化物相比，采用催化氢化或转移氢化的方法将羰基酮类化合物转换成醇类化合物更加绿色环保。
转移氢化反应(TH)是一种具有吸引力、可持续的化学计量还原方法。金属配合物催化氢化和氢转移反应是学术界和化工界中应用最广泛、最基本的还原反应之一(Chem.Rev.2015,115,13,6621)。其中，钼作为国内储量丰富、生物兼容性好的有色金属，在冶炼、探测、航天、医学、催化剂和陶瓷等领域有着广泛的应用。随着金属与配体协同作用催化机制(Acc.Chem.Res.2015,48,1979；Chem.Rev.2019,119,2681)的提出，人们发现钳形配体与钼金属可形成钳形钼配合物并应用于催化反应。但钳形钼配合物在均相催化氢化领域发展较为缓慢，仅有几例钼催化剂用于亚胺/腈(ACS Catal.2014,4,2191；ACSCatal.2020,10,380)、酮(Organometallics 2018,37,4402,Organometallics 2020,39,4535)和酰胺(Chem Sci 2019,10,10566)的氢化。
Figure BDA0003048038640000011
目前研究的酮催化氢化的钼金属催化剂(如上式所示)，主要有以下几种催化体系如下：Darensbourg等(J.Am.Chem.Soc.1986,108,5465)发展的钼加合物1[PPN(双(三苯基正膦基)氯化铵)Mo(CO)5(OAc)]并用于催化氢化醛酮的反应中：使用5mol％1为催化剂，在47.3bar H2，125℃下，将环己酮和苯甲醛还原成相应的醇；Kuo等(Organometallics 2003,22,2422)将二茂钼催化剂2[(Cp2-Mo(μ-OH)2MoCp2)(OTs)2]用于苯乙酮的转移氢化反应：以2.5eq.KOH做助催化剂，82℃，氘代异丙醇为氢源，可在12h内将苯乙酮转化成苯乙醇；Bullock组(Organometallics 2005,24,6220)报道了单膦茂钼催化剂3用于催化氢化酮成醇：以Ph3C+BAr'4 +三苯碳四(苯基)硼酸盐为助剂，56bar H2，无溶剂还原成3-戊酮成3-戊醇；Beller等(Organometallics 2018,37,4402)将双(2-(二异丙基膦基)乙基)胺与羰基钼络合形成催化剂4用于酮和烯烃的氢化反应：以三乙基硼氢化钠(NaHBEt3)为添加剂，56barH2，80℃，该体系在16h内将7例苯乙酮及其衍生物转化成相应的醇；Topf等(Organometallics 2020,39,4535-4543)发展了二齿氮膦钼配合物用于催化羰基酮的氢化反应：在t-BuOK做助剂，40bar H2，仅有苯乙酮4％的转化率。
当前，由于钼基催化体系面临着催化剂活性不高、底物适用范围窄、反应条件较苛刻等困难和挑战，难以进一步工业化应用，因此设计合成新的配体，调控配体的电子效应和位阻效应，调节钼中心的反应性和稳定性，从而开发出催化活性和选择性更高的氢化催化剂是钼催化剂当前发展的必要趋势。
发明内容
本发明的目的是提供一种钳形钼配合物，该钳形钼配合物在催化酮转移氢化成醇的过程中，表现出催化剂活性高、底物适用范围宽、反应条件温和等优良的催化性能。
为了实现上述目的，本发明采取如下技术方案：
钳形钼配合物，为2-(Y取代基乙基)-(5,6,7,8-四氢喹啉基)胺羰基钼化合物，结构如式Ⅰ所示：
Figure BDA0003048038640000021
其中，Y为NMe2、NEt2、Ni-Pr2、Nt-Bu、NHMe、NHEt、SMe、SEt、SPh、SBn、OMe、OEt、PPh2、Pi-Pr2或Pt-Bu2；X1、X2彼此独立为CO、Cl、Br、I、PPh3或AsPh3。
优选的，所述Y为NMe2、NEt2、Ni-Pr2或SEt；所述X1、X2彼此独立为CO、Br、I或PPh3。
进一步优选的，所述X1为CO，所述X2为CO，所述Y为NMe2；
或者所述X1为CO，所述X2为CO，所述Y为NEt2；
或者所述X1为CO，所述X2为CO，所述Y为Ni-Pr2；
或者所述X1为CO，所述X2为Br，所述Y为NMe2；
或者所述X1为CO，所述X2为Br，所述Y为NEt2；
或者所述X1为CO，所述X2为Br，所述Y为Ni-Pr2；
或者所述X1为PPh2，所述X2为PPh2，所述Y为NMe2；
或者所述X1为CO，所述X2为PPh2，所述Y为Ni-Pr2；
或者所述X1为PPh2，所述X2为PPh2，所述Y为SEt。
本发明的另一个目的是提供上述钳形钼配合物的制备方法，并采取如下方案：
将式Ⅱ所示结构的配体与钼金属前体进行反应，得到式Ⅰ所示结构的所述钳形钼配合物：
Figure BDA0003048038640000031
其中，所述钼金属前体为Mo(CO)6、Mo(CO)3(MeCN)3、Mo(η3-C3H5)(CO)2(MeCN)2Br、Mo(PPh3)2(CO)2(MeCN)2、[Cp-Mo(CO)3]2；Y为NMe2、NEt2、Ni-Pr2、Nt-Bu、NHMe、NHEt、SMe、SEt、SPh、SBn、OMe、OEt、PPh2、Pi-Pr2或Pt-Bu2；X1、X2彼此独立为CO、Cl、Br、I、PPh3或AsPh3
其中，式Ⅱ所示结构的配体与钼金属前体的摩尔比为1:0.8～1.5；反应的溶剂选自乙醚、四氢呋喃(THF)、2-甲基四氢呋喃、甲苯、二甲苯、二氯甲烷、乙腈的一种或几种混合，优选甲苯；反应温度为30～140℃，如110℃；反应时间为6～48小时，如12小时；反应优选在惰性气体氛围中进行，例如在氮气氛围下进行。
本发明的另一个目的是提供一种催化剂组合物，该催化剂组合物以上述钳形钼配合物作为活性成分，并辅以助剂制成。
优选的，所述助剂为t-BuOK、t-BuONa、i-PrONa、EtONa、MeONa、KOH、NaOH、NaHBEt3、K2CO3、Na2CO3等有机或无机碱中的一种或多种组合。
或者进一步优选的，所述助剂为NaOH和/或NaHBEt3，且NaOH、NaHBEt3与所述钳形钼配合物中的Mo的摩尔比为0～1000:0～20:1，例如为0:10:1，10:0:1，10:10:1，50:10:1，100:10:1，200:10:1，400:10:1或1000:20:1。
本发明还提供上述催化剂组合物在催化酮转移氢化成醇的反应中的应用。
本发明的最后一个目的是提供一种醇的制备方法，所述醇由酮在上述钳形钼配合物或催化剂组合物的催化下进行转移氢化所得，反应式如下：
Figure BDA0003048038640000032
R1、R2彼此独立地选自C1-6烷基、C3-15环烷基、C6-14芳基或杂芳基，反应的温度为0～140℃，。
本发明所述制备方法包括以下步骤：
在氮气氛围下，在Schlenk反应瓶中将钼金属前体(式Ⅲ)和相应的配体(式Ⅱ，L1L4)溶于合适的有机溶剂中。反应混合物在适合的温度下搅拌12h后，得到的悬浮液冷却至室温后，减压浓缩一部分有机试剂，过滤得到沉淀物，分别用甲苯、正己烷洗涤沉淀物，并将沉淀溶解在二氯甲烷中，加入大量干燥的乙醚，析出大量固体产物。过滤得到固体，用乙醚洗涤，在真空下干燥，得到钼配合物(式Ⅰ，Mo-1～Mo-9)。
本发明还提供式Ⅰ所示钼配合物的应用，即式Ⅳ所示酮类催化化合物转移氢化成式Ⅴ所示醇类化合物，如下所示：
Figure BDA0003048038640000041
其中，R1、R2相同或不同，彼此独立地选自C1-6烷基、C3-15环烷基、C6-14芳基、杂芳基；
本发明提供一系列催化剂组合物，包括如上述式Ⅰ所示钼配合物；
优选地，所述催化剂组合物用于催化羰基酮转移氢化反应；
任选地，所述催化剂组合物还包括助催化剂；
优选地，所述助催化剂可以选自t-BuOK、t-BuONa、i-PrONa、EtONa、MeONa、KOH、NaOH、NaHBEt3、K2CO3、Na2CO3等有机或无机碱中的一种或多种组合；
根据本发明，所述助催化剂具体选用NaOH和NaHBEt3的组合物；
当所述催化剂组合物还包括助催化剂，所述助催化剂中NaOH和NaHBEt3与式I所示化合物中的Mo的摩尔比为0～1000:0～20:1，例如为0:10:1，10:0:1，10:10:1，50:10:1，100:10:1，200:10:1，400:10:1或1000:10:1；
优选地，当所述助催化剂为NaOH和NaHBEt3，NaOH和NaHBEt3中钠与式Ⅰ所示化合物中的Mo的摩尔比为(10～500):(0～20):1，优选摩尔比为200:10:1。
所述转移氢化反应的温度为0～140℃，例如为30～110℃，如为30℃、0℃、60℃、90℃或110℃；所述转移氢化反应的时间为1～48h，例如1～6h，如为2h；反应溶剂选自甲醇、乙醇、异丙醇、异丁醇、叔丁醇、异戊醇等醇类溶剂等质子溶剂的一种或两种，例如选自异丙醇、异丁醇和异戊醇中的一种或多种，如异丙醇。
以上化学式中，Me代表甲基，Et代表乙基，i-Pr代表异丙基，t-Bu代表叔丁基。
本发明提供的钳形钼配合物将环烷基环引入配体骨架中，通过调控环烷基环的环张力、柔韧性和空间位阻，可有效调节钼金属中心的反应性和稳定性，显著提高了钼金属体系的催化活性和底物适用性。以该钳形钼配合物为活性成分的催化剂组合物在催化酮转移氢化成醇的反应中，催化活性高、底物适用范围广，催化剂负载量低至0.4mol％，并且催化反应具有清洁、环保、绿色、安全、高效的优点。钳形钼金属配合物的制备方法具有反应条件温和、周期短、操作条件简单等优点。鉴于上述优点及钼金属在国内储量丰富、生物兼容性好，本钳形钼配合物具有广泛的应用前景和经济价值。
附图说明
图1是Mo-1的单晶图。
具体实施方式
除非另有定义，本文所有科技术语的涵义与所属领域技术人员通常理解的涵义相同。应理解，上述简述和下文的详述为示例性且仅用于解释，而不对本发明作任何限制。
术语“C1-6烷基”指具有1-6个碳的烷基，包括直链或支链烷基，例如为甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基、仲丁基、戊基、新戊基、己基等。
术语“C6-14芳基”表示具有6～14个碳原子的芳香性或部分芳香性的单环、双环或三环烃，如具有6、7、8、9、10、11、12、13或14个碳原子的一价芳香性或部分芳香性的单环、双环或三环烃，特别是具有6个碳原子的环(“C6芳基”)，例如苯基；或联苯基，或者是具有9个碳原子的环(“C9芳基”)，例如茚基，或者是具有10个碳原子的环(“C10芳基”)，例如四氢化萘基、二氢萘基或萘基，或者是具有13个碳原子的环(“C13芳基”)，例如芴基，或者是具有14个碳原子的环(“C14芳基”)，例如蒽基。
术语“杂芳基”应理解为含有5-20个环原子、5-14个环原子，或5-12个环原子，或5-10个环原子，或5-6个环原子的单环、双环和三环体系，其中至少一个环体系是芳香族的，且至少一个环体系包含一个或多个杂原子(例如N、O、S、Se等)。所述杂芳基基团任选地被一个或多个本发明所描述的取代基所取代。在一些实施例中，5-10个原子组成的杂芳基包含1,2,3或4个独立选自O、S、Se和N的杂原子。在另一些实施例中，5-6个原子组成的杂芳基包含1,2,3或4个独立选自O、S、Se和N的杂原子。
杂芳基的单环实例包括，但并不限于，噻吩基、呋喃基、吡咯基、噁唑基、噻唑基、咪唑基、吡唑基、异噁唑基、异噻唑基、噁二唑基、三唑基、噻二唑基、噻-4H-吡唑基等以及它们的苯并衍生物，例如苯并呋喃基、苯并噻吩基、苯并噁唑基、苯并异噁唑基、苯并咪唑基、苯并三唑基、吲唑基、吲哚基、异吲哚基等；或吡啶基、哒嗪基、嘧啶基、吡嗪基、三嗪基等，以及它们的苯并衍生物，例如喹啉基、喹唑啉基、异喹啉基等；或吖辛因基、吲嗪基、嘌呤基等以及它们的苯并衍生物；或噌啉基、酞嗪基、喹唑啉基、喹喔啉基、萘啶基、蝶啶基、咔唑基、吖啶基、吩嗪基、吩噻嗪基、吩噁嗪基等。
下面结合具体实施例对本发明作进一步阐述，但本发明并不限于以下实施例。所述方法如无特别说明均为常规方法，所有的操作使用Schlenk技术在氮气气氛下进行，所有的溶剂在使用之前进行蒸馏处理。所述原材料如无特别说明均能从公开商业途径而得。
所用碱助催化剂(NaOH，KOH，t-BuOK，NaHBEt3等)从伊诺凯、阿拉丁、麦克林、安耐吉、毕得医药、江苏艾康生物医药等试剂公司购买。所用钼金属前体Mo(CO)6、Mo(η3-C3H5)(CO)2(MeCN)2Br Mo(PPh3)2(CO)2(MeCN)2均购自安耐吉。
实施例1制备下式所示Mo-1
Figure BDA0003048038640000051
在Schlenk瓶中将N1,N1-二甲基-N2-(5,6,7,8-四氢喹啉-8-基)乙烷-1,2-二胺(0.219g,1mmol)和六羰基钼(Mo(CO)6，0.265g，1mmol)溶于10mL甲苯中，将混合物在110℃搅拌反应12小时，将得到的黄红色悬浮液冷却至室温，减压整除部分甲苯，悬浮液过滤得到黄色沉淀，分别用甲苯(2×2mL)、正己烷(2×2mL)洗涤，之后沉淀物溶解于少量二氯甲烷中，加入大量干燥乙醚析出黄色固体。将过滤得到的沉淀用5mL乙醚洗涤两次，在真空下干燥，得到0.325g(81％)的Mo-1，为黄色固体。结构确证数据如下：1H NMR(500MHz,DMSO-d)δ8.67(d,J＝4.7Hz,1H),7.67(d,J＝7.6Hz,1H),7.31(dd,J＝7.6,5.4Hz,1H),5.78(s,1H),4.21–4.15(m,1H),2.80–2.76(m,3H),2.74(s,3H),2.46(s,1H),2.15(d,J＝9.1Hz,1H),2.08–2.01(m,1H),1.99-1.93(m,3H),1.90(s,3H),1.75(dd,J＝14.3,6.5Hz,1H)；13C NMR(100MHz,DMSO-d)δ157.67,150.02,138.38,135.78,123.67,62.73,61.57,55.90,47.50,42.32,28.02,26.96,21.38；ⅠR(ATR,cm-1,KBr):1728(s,ⅤCO),1771(s,vCO),1897(s,vCO)；元素分析：Mo-1(399.31)[C16H21MoN3O3]理论值：C,48.13；H,5.30；N,10.52％；实验值：C,48.11,H,5.34,N,10.45％。
晶体结构示意图如图1所示。
由图1可知，配合物Mo-1的中心金属Mo采用六配位模式，分别与三个氮原子N1，N2，N3和三个羰基碳C14、C15、C16相连，呈变形扭曲八面体结构。选定的键长
Figure BDA0003048038640000063
和键角(deg)：Mo1-N1＝2.2706(15)，Mo1-N2＝2.2952(15)，Mo1-N3＝2.3677(15)，Mo1-C15＝1.943(2)，Mo1-C14＝1.926(2)，Mo1-C16＝1.941(2)，N1-Mo1-N2＝72.07(6)，N1-Mo1-N3＝88.62(5)，C15-Mo1-N1＝103.95(7)，C14-Mo1-N1＝91.52(7)，C16-Mo1-N1＝169.88(7)。
实施例2制备下式所示Mo-2
Figure BDA0003048038640000061
在Schlenk瓶中将N1,N1-二乙基-N2-(5,6,7,8-四氢喹啉-8-基)乙烷-1,2-二胺(0.247g,1mmol)和六羰合钼(Mo(CO)6，0.265g,1mmol)溶于10mL甲苯溶剂，将混合物在110℃搅拌反应12小时，将得到的黄红色悬浮液冷却至室温，减压整除部分甲苯，悬浮液过滤得到黄色沉淀，分别用甲苯(2×2mL)、正己烷(2×2mL)洗涤，之后沉淀物溶解于少量二氯甲烷中，加入大量干燥乙醚析出黄色固体。将过滤得到的沉淀用5mL乙醚洗涤两次，在真空下干燥，得到0.375g(87％)的Mo-2，为黄色固体。
结构确证数据如下：
1H NMR(500MHz,DMSO-d)δ8.64(d,J＝4.3Hz,1H),7.66(d,J＝7.4Hz,1H),7.31(dd,J＝7.6,5.4Hz,1H),5.77(s,1H),4.21–4.12(m,1H),3.25-3.21(m,1H),2.94–2.90(m,1H),2.77(d,J＝6.7Hz,3H),2.43(d,J＝11.5Hz,1H),2.31(d,J＝7.9Hz,1H),2.17-2.13(m,1H),2.07-2.03(m,1H),2.00–1.92(m,2H),1.92–1.83(m,2H),1.81-1.74(m,1H),1.09(t,J＝7.2Hz,3H),0.98(t,J＝7.1Hz,3H)；13C NMR(125MHz,DMSO-d)δ159.38,151.84,140.32,136.12,125.65,64.15,57.33,54.23,27.39,26.38,21.29,10.78,8.37；ⅠR(ATR,cm-1,KBr):1728(s,vCO),1775(s,vCO),1894(s,vCO)；元素分析：Mo-2(327.37)[C18H25MoN3O3]理论值：C,50.59；H,5.90；N,9.83％；实验值：C,50.61,H,5.94,N,9.75％。
实施例3制备下式所示Mo-3
Figure BDA0003048038640000062
在Schlenk瓶中将N1,N1-二异丙基-N2-(5,6,7,8-四氢喹啉-8-基)乙烷-1,2-二胺(0.275g,1mmol)和六羰基钼(0.265g,1mmol)溶于10mL甲苯溶剂，将混合物在110℃下搅拌反应12小时，将得到的黄红色悬浮液冷却至室温，减压整除部分甲苯，悬浮液过滤得到黄色沉淀，分别用甲苯(2×2mL)、正己烷(2×2mL)洗涤，之后沉淀物溶解于少量二氯甲烷中，加入大量干燥乙醚析出黄色固体。将过滤得到的沉淀用5mL乙醚洗涤两次，在真空下干燥，得到0.415g(91％)的Mo-3，为黄色固体。
结构确证数据如下：
1H NMR(500MHz,DMSO-d)δ8.59(d,J＝4.7Hz,1H),7.71(d,J＝7.5Hz,1H),7.31(dd,J＝7.6,5.4Hz,1H),4.52–4.45(m,1H),3.84(s,1H),3.08–2.94(m,4H),2.82-2.65(m,4H),1.99(d,J＝10.6Hz,1H),1.78–1.72(m,1H),1.54(dd,J＝23.1,11.1Hz,1H),1.20(d,J＝6.5Hz,1H),1.01(dd,J＝13.3,6.5Hz,12H)；13CNMR(100MHz,DMSO-d)δ208.91(C＝O),206.71(C＝O),158.61,150.11,138.93,135.63,123.67,64.35,48.74,46.77,44.32,28.16,27.67,21.15,20.56,19.29；ⅠR(ATR,cm-1,KBr):1815(s,vCO),1861(s,vCO),2006(s,vCO)；元素分析：Mo-3(455.42)[C20H29MoN3O3]理论值：C,52.75；H,6.42；N,9.23％；实验值：C,52.63,H,6.58,N,9.18％。
实施例4制备下式所示Mo-4
Figure BDA0003048038640000071
在Schlenk瓶中加入N1,N1-二甲基-N2-(5,6,7,8-四氢喹啉-8-基)乙烷-1,2-二胺(0.219g,1mmol)和钼金属前体Mo(η3-C3H5)(CO)2(MeCN)2Br(0.355g,1mmol)溶于10mL甲苯中，将反应混合物在30℃下搅拌反应16小时。将得到的黄色悬浮液减压浓缩至3mL，过滤得黄棕色固体，分别用甲苯(2×2mL)、正己烷(2×2mL)洗涤，之后沉淀物溶解于少量二氯甲烷中，加入大量干燥乙醚析出黄色固体。将过滤得到的沉淀用5mL乙醚洗涤两次，在真空干燥得到0.310g(68％)的Mo-4，为浅棕色粉末。
结构确证数据如下：
1H NMR(500MHz,DMSO-d)δ8.49(br,1H),7.83(d,J＝7.0Hz,2H),7.51-7.48(m,2H),4.58(s,1H),4.21(br,1H),2.94–2.91(m,2H),2.85-2.76(m,2H),2.56(s,3H),2.21-2.18(m,2H),2.06-2.02(m,2H),1.79(s,3H),1.41–1.19(m,2H)；13C NMR(125MHz,DMSO-d)δ157.04,149.77,143.08,136.15,125.54,60.69,59.95,53.65,49.96,41.97,27.84,26.38,21.10；ⅠR(ATR,cm-1,KBr):1841(s,vCO),1934(s,vCO)；元素分析：Mo-4(451.21)[C15H21BrMoN3O2]理论值：C,39.93；H,4.69；N,9.31％；实验值：C,39.98,H,4.71,N,9.28％。
实施例5制备下式所示Mo-5
Figure BDA0003048038640000072
在Schlenk瓶中加入N1,N1-二甲基-N2-(5,6,7,8-四氢喹啉-8-基)乙烷-1,2-二胺(0.247g,1mmol)和钼金属前体Mo(η3-C3H5)(CO)2(MeCN)2Br(0.355g,1mmol)溶于10mL甲苯中，将混合物在30℃下搅拌反应16小时，获得黄色悬浮液，将溶剂真空浓缩至3mL，悬浮液过滤得到黄色沉淀，分别用甲苯(2×2mL)、正己烷(2×2mL)洗涤，之后沉淀物溶解于少量二氯甲烷中，加入大量干燥乙醚析出黄色固体。再用5mL乙醚洗涤两次，在真空干燥得到0.365g(76％)的Mo-5，为浅棕色粉末。
结构确证数据如下：
1H NMR(500MHz,DMSO)δ8.49–8.45(m,1H),7.67(d,J＝7.5Hz,1H),7.39–7.34(m,1H),3.71(d,J＝10.3Hz,1H),3.17–3.11(m,2H),3.06–3.00(m,2H),2.82(s,4H),2.65–2.63(m,1H),2.37–2.36(m,1H),2.30(s,1H),2.02(s,1H),1.84–1.77(m,2H),1.26(s,3H),1.21(d,J＝6.4Hz,3H)；13C NMR(125MHz,DMSO-d)δ152.19,147.01,138.24,138.16,133.63,123.92,59.20,57.03,50.34,46.97,42.32,27.71,26.02,20.36,19.92；ⅠR(ATR,cm-1,KBr):1908(s,vCO),2025(s,vCO)；元素分析：Mo-5(479.26)[C17H25BrMoN3O2]理论值：C,42.60；H,5.26；N,8.77％；实验值：C,42.51,H,5.30,N,8.68％。
实施例6制备下式所示Mo-6
Figure BDA0003048038640000081
在Schlenk瓶中加入N1,N1-二异丙基-N2-(5,6,7,8-四氢喹啉-8-基)乙烷-1,2-二胺(0.275g,1mmol)和钼金属前体Mo(η3-C3H5)(CO)2(MeCN)2Br(0.355g,1mmol)溶于10mL甲苯中，将混合物在30℃下搅拌反应16小时。获得黄色悬浮液，将溶剂真空浓缩至3mL，悬浮液过滤得到黄色沉淀，分别用甲苯(2×2mL)、正己烷(2×2mL)洗涤，之后沉淀物溶解于少量二氯甲烷中，加入大量干燥乙醚析出黄色固体。将过滤得到的沉淀用5mL乙醚洗涤两次，在真空干燥得到0.410g(72％)的Mo-6，为浅棕色粉末。
结构确证数据如下：
1H NMR(400MHz,DMSO-d)δ8.45-8.25(m,1H),7.77–7.65(m,1H),7.52–7.29(m,1H),4.39(s,1H),3.90–3.59(m,2H),3.36(ddd,J＝15.3,10.9,5.0Hz,2H),3.17–3.05(m,2H),2.83–2.75(m,2H),2.03(dd,J＝17.4,11.6Hz,1H),1.87–1.72(m,1H),1.35(s,1H),1.19(dd,J＝18.7,7.9Hz,1H),1.05(d,J＝6.4Hz,12H)；13C NMR(125MHz,DMSO-d)δ155.70,149.31,139.44,134.70,125.19,65.38,62.49,56.81,53.58,48.55,28.06,27.82,21.39,20.78,15.64；ⅠR(ATR,cm-1,KBr):1846(s,vCO),1930(s,vCO)；元素分析：Mo-6(507.31)[C19H29BrMoN3O2]理论值：C,44.98；H,5.76；N,8.28％；实验值：C,44.91,H,5.83,N,8.24％。
实施例7制备下式所示Mo-7
Figure BDA0003048038640000082
在Schlenk瓶中将N1,N1-二甲基-N2-(5,6,7,8-四氢喹啉-8-基)乙烷-1,2-二胺(0.219g,1mmol)和钼金属前体Mo(PPh3)2(CO)2(MeCN)2(0.758g,1mmol)溶于10mL二氯甲烷中，将混合物在室温下搅拌反应12小时。混合物减压浓缩至2mL，加入大量乙醚析出浅黄色沉淀，浅黄色固体用5mL乙醚洗涤两次，真空干燥得到0.462g(53％)的Mo-7,产物为浅黄色粉末。
结构确证数据如下：
1H NMR(500MHz,DMSO)δ8.72(d,J＝5.1Hz,1H),7.82(d,J＝7.7Hz,1H),7.65–7.60(m,18H),7.56(dd,J＝7.1,3.0Hz,12H),7.48–7.46(m,1H),6.43(s,1H),4.25–4.18(m,1H),2.86(s,3H),2.83–2.80(m,2H),2.16(dd,J＝9.4,2.9Hz,2H),2.07(d,J＝12.4Hz,2H),2.00–1.96(m,1H),1.90(d,J＝11.8Hz,1H),1.80–1.71(m,2H),1.66(s,3H)；13C NMR(100MHz,DMSO-d)δ158.19,157.22,156.12,149.69,148.43,146.91,146.23,143.02,140.37,137.90,137.05,135.81,135.53,135.17,134.36,134.25,134.00,132.98,132.38,132.36,131.99,131.90,130.85,130.72,129.18,129.07,128.92,128.81,126.16,123.86,122.60,122.20,60.87,58.36,53.63,49.89,45.65,27.60,25.77,21.13,19.47；31P NMR(202MHz,DMSO-d)δ25.67,17.44；ⅠR(ATR,cm-1,KBr):1886(s,vCO)；元素分析：Mo-7(867.88)[C50H51MoN3OP2]理论值：C,69.20；H,5.92；N,4.84％；实验值：C,69.16,H,5.98,N,4.76％。
实施例8制备下式所示Mo-8
Figure BDA0003048038640000091
在Schlenk瓶中将N1,N1-二异丙基-N2-(5,6,7,8-四氢喹啉-8-基)乙烷-1,2-二胺(0.275g,1mmol)和钼金属前体Mo(PPh3)2(CO)2(MeCN)2(0.758g,1mmol)溶于10mL二氯甲烷中，将反应混合物在室温下搅拌反应12小时。真空浓缩溶剂至2mL，加入大量乙醚析出浅黄色沉淀，浅黄色固体用5mL乙醚洗涤两次，真空干燥得到0.565g(82％)的Mo-8，为浅黄色粉末。
结构确证数据如下：
1H NMR(500MHz,DMSO-d)δ8.46(d,J＝3.8Hz,1H),7.78(dd,J＝7.8,4.2Hz,1H),7.68–7.60(m,10H),7.57–7.54(m,7H),7.35(dd,J＝7.6,4.6Hz,1H),4.37(s,1H),3.15–3.11(m,2H),3.03(s,2H),2.82(d,J＝6.9Hz,4H),2.31(s,1H),2.16(d,J＝6.5Hz,1H),2.00(d,J＝5.0Hz,1H),1.82–1.77(m,1H),1.05(d,J＝6.5Hz,12H)；13C NMR(125MHz,DMSO-d)δ199.77(C＝O),193.89(C＝O),152.17,147.06,138.29,135.56,134.37,134.29,133.55,132.73,132.54,132.53,131.98,131.90,130.87,130.77,129.28,129.19,129.14,129.04,128.93,123.97,119.30,56.87,48.96,46.82,43.50,27.70,25.89,20.83,20.25,20.02,19.27；31P NMR(202MHz,DMSO-d)δ25.55；ⅠR(ATR,cm-1,KBr):1889(s,vCO),1942(s,vCO)；元素分析：Mo-8(689.70)[C37H44MoN3O2P]理论值：C,64.43；H,6.43；N,6.09％；实验值：C,64.42,H,6.48,N,6.01％。
实施例9制备下式所示Mo-9
Figure BDA0003048038640000092
在Schlenk瓶中将N1,N1-二异丙基-N2-(5,6,7,8-四氢喹啉-8-基)乙烷-1,2-二胺(0.275g,1mmol)和钼金属前体Mo(PPh3)2(CO)2(MeCN)2(0.758g,1mmol)溶于10mL二氯甲烷中，将混合物在室温下搅拌反应12小时。真空浓缩溶剂至2mL，加入乙醚(20mL)直至出现产物沉淀，过滤出浅黄色固体，用5mL乙醚洗涤两次，真空干燥得到0.546g(67％)的Mo-9，为浅黄色粉末。
结构确证数据如下：
1H NMR(500MHz,DMSO)δ8.45(s,1H),8.11(s,1H),7.95–7.88(m,3H),7.84–7.76(m,5H),7.75–7.69(m,4H),7.62(dd,J＝11.7,7.1Hz,5H),7.58–7.52(m,3H),7.48(d,J＝3.2Hz,6H),7.44(d,J＝5.2Hz,2H),7.31(s,2H),7.20–7.16(m,1H),3.03–3.01(m,1H),2.79(s,4H),2.56(d,J＝7.3Hz,2H),2.16(d,J＝6.2Hz,2H),2.01(s,2H),1.75(s,2H),1.21(s,3H)；13C NMR(100MHz,DMSO-d)δ203.98(C＝O),151.88,147.09,144.41,139.34,138.30,138.11,137.44,137.32,135.49,134.36,134.25,134.06,133.80,133.60,133.04,132.92,132.80,132.35,132.33,131.99,131.89,130.84,130.71,129.43,129.34,129.16,129.09,129.05,128.79,124.07,123.95,56.93,47.22,45.12,34.88,32.69,27.71,25.44,19.82,15.10；31P NMR(202MHz,DMSO-d)δ50.65,17.36；ⅠR(ATR,cm-1,KBr):1888(s,vCO)；元素分析：Mo-9(807.81)[C44H45MoN2OP2S]理论值：C,65.42；H,5.62；N,3.47％；实验值：C,65.48,H,5.68,N,3.46％。
实施例10配合物Mo-8作为催化剂在催化苯乙酮转移氢化成苯乙醇的应用，如下反应式(1)。
Figure BDA0003048038640000101
在Schlenk瓶中依次加入0.30g(2.5mmol)苯乙酮，0～2.5mmol(0～1eq.)碱助剂，0～6.1mg(0～10μmmol，0.4mol％)Mo-8，0～0.1mL(0～0.1mmol)NaBHEt3(1M in THF)，5mL干燥的异丙醇，使用双排管排除体系空气，并充入氮气。在90℃(油浴温度)中加热搅拌反应2h。反应体系冷却，经GC检测分析(以十二烷为内标物)结果如表一所示。
表一 碱对氢化效率的影响a
Figure BDA0003048038640000102
a反应条件：0.30g(2.5mmol)苯乙酮，0～6.1mg(0～10μmol)Mo-8，0～2.5mmol(0～1eq.)碱助剂，0～0.1mmol(0～4mol％)NaBHEt3，5mL i-PrOH，90℃，2h；b以十二烷为内标，GC检测确定；c 2.0mmol NaOH(80mol％)。
由表一可知以NaOH和NaHBEt3作组合碱助剂，温度90℃，反应2h，该钼体系显示出良好的催化活性，转化率达95％，苯乙醇收率可达95％。
实施例11以配合物Mo-8作为催化剂在催化苯乙酮转移氢化成苯乙醇的应用，如下反应式(2)：
Figure BDA0003048038640000103
在Schlenk瓶中依次加入0.30g(2.5mmol)苯乙酮，10mg(2.5mmol,1eq.)NaOH，6.1mg(10μmmol，0.4mol％)Mo-8，0.1mL(0.1mmol)NaBHEt3(1M in THF)，5mL干燥的异丙醇，使用双排管排除体系中空气，并充入氮气。在20～110℃(油浴温度)搅拌反应2h，反应体系冷却，经GC检测分析(以十二烷为内标物)结果如表二所示。
表二 温度对苯乙酮转移氢化的影响
Figure BDA0003048038640000111
a反应条件：0.30g(2.5mmol)苯乙酮，6.1mg(10μmol)Mo-8，10mg(2.5mmol,1eq.)
NaOH，0.1mmol(4mol％)NaBHEt3，5mL i-PrOH，90℃，2h；b以十二烷为内标，GC
检测确定。
实施例12钼体系催化苯乙酮转移氢化成苯乙醇的应用，如下反应式(3)：
Figure BDA0003048038640000112
在Schlenk瓶中依次加入0.30g(2.5mmol)苯乙酮，10mg(2.5mmol,1eq.)NaOH，10μmmol(0.4mol％)Mo1～Mo9，0.1mL(0.1mmol)NaBHEt3(1M in THF)，5mL干燥的异丙醇，使用双排管排除体系中空气，并充入氮气。在90℃(油浴温度)搅拌反应2h，反应体系冷却，经GC检测分析(以十二烷为内标物)结果如表三所示。
表三 催化剂对苯乙酮转移氢化的影响
Figure BDA0003048038640000113
a反应条件：0.30g(2.5mmol)苯乙酮，10μmol[Mo]，10mg(2.5mmol,1eq.)NaOH，0.1mmol
(4mol％)NaBHEt3，5mL i-PrOH，90℃，2h；b以十二烷为内标，GC检测确定；cMo-10为Mo(CO)6；dMo-11为Mo(PPh3)2(CO)2(MeCN)2；eMo-12为Mo(n-C3H5)Br(CO)2(MeCN)2。
Figure BDA0003048038640000121
实施例13Mo-8在催化芳香族酮转移氢化成芳香醇的应用，如下反应式(4)：
Figure BDA0003048038640000122
在Schlenk瓶中依次加入2.5mmol芳香族酮，10～20mg(2.5～5.0mmol,1～2eq.)NaOH，10μmmol(0.4mol％)Mo-8，0.1mL(0.1mmol)NaBHEt3(1M in THF)，5mL干燥的异丙醇，使用双排管排除体系中空气，并充入氮气。在90℃(油浴温度)搅拌反应2～5h，反应体系冷却，经GC检测分析(十二烷为内标)芳香族酮的转化率与还原醇的收率如表四所示。
表四：不同芳基酮的转移氢化反应a
Figure BDA0003048038640000123
Figure BDA0003048038640000131
Figure BDA0003048038640000141
a反应条件：2.5mmol芳香族酮，10μmol Mo-8，10mg(2.5mmol,1eq.)NaOH，0.1mmol(4mol％)NaBHEt3，5mL i-PrOH，90℃，2h；b以十二烷为内标，GC检测确定；c20mg(5.0mmol,2eq.)NaOH。
从表四中可以看出，钼配合物Mo-8对底物的苯环上具有吸电子基团的取代基具有更高的催化活性。尤其对卤原子中的氯原子和溴原子的卤代苯乙酮衍生物。
实施例14Mo-8在催化脂肪族酮转移氢化成脂肪醇的应用，如下反应式(5)。
Figure BDA0003048038640000142
在Schlenk瓶中依次加入催化剂Mo-8 0.4mol％(S/C＝250)、2.5mmol反应物、1当量NaOH、助催化剂0.01220g(0.1mmol)NaBHEt3(4mol％)、溶剂5mL，使用双排管排除体系中空气，并充入氮气。在90℃(油浴温度)搅拌反应2～5h，反应体系冷却，经GC检测分析(十二烷为内标)芳香族酮的转化率与还原醇的收率如表四所示。
表五 不同脂肪族酮的转移氢化反应a
Figure BDA0003048038640000143
Figure BDA0003048038640000151
a反应条件：2.5mmol脂肪族酮，10μmol Mo-8，10mg(2.5mmol,1eq.)NaOH，0.1mmol(4mol％)NaBHEt3，5mL i-PrOH，90℃，2h；b以十二烷为内标，GC检测确定；c20mg(5.0mmol,2eq.)NaOH。
从表五中可以看出，钼配合物Mo-8对脂肪族环烷基酮的催化活性有一定差异性。对环己酮及其衍生物转化率高，如环己酮，转化率达98％，收率98％。

Claims (8)

1.钳形钼配合物，结构如式Ⅰ所示：
Figure 676170DEST_PATH_IMAGE001
其中，Y为NMe2、NEt2、N i- Pr2、NHMe、NHEt、SMe、SEt、SPh、SBn、OMe、OEt、PPh2、P i- Pr2或P t- Bu2；X1、X2彼此独立为CO、Cl、Br、I、PPh3或AsPh3。
2.如权利要求1所述的钳形钼配合物，其特征在于，所述Y为NMe2、NEt2、N i- Pr2或SEt；所述X1、X2彼此独立为CO、Br、I或PPh3。
3.如权利要求1所述的钳形钼配合物，其特征在于，
所述X1 为 CO，所述X2 为 CO，所述Y为NMe2；
或者所述X1为 CO，所述X2 为 CO，所述Y为NEt2；
或者所述X1 为 CO，所述X2为 CO，所述Y为N i- Pr2；
或者所述X1 为 CO，所述X2 为 Br，所述Y为NMe2；
或者所述X1为 CO，所述X2 为 Br，所述Y为NEt2；
或者所述X1 为 CO，所述X2 为 Br，所述Y为N i- Pr2；
或者所述X1为PPh3，所述X2为 PPh3，所述Y为NMe2；
或者所述X1 为CO，所述X2 为 PPh3，所述Y为N i- Pr2；
或者所述X1 为PPh3，所述 X2 为PPh3，所述Y为SEt。
4.如权利要求1所述的钳形钼配合物的制备方法，其特征在于，将式Ⅱ所示结构的配体与钼金属前体进行反应，得到式Ⅰ所示结构的所述钳形钼配合物：
Figure 128011DEST_PATH_IMAGE002
其中，所述钼金属前体为Mo(CO)6、Mo(CO)3(MeCN)3、Mo(η3-C3H5)(CO)2(MeCN)2Br或Mo(PPh3)2(CO)2(MeCN)2；Y为NMe2、NEt2、N i- Pr2、NHMe、NHEt、SMe、SEt、SPh、SBn、OMe、OEt、PPh2、P i- Pr2或P t- Bu2；X1、X2彼此独立为CO、Cl、Br、I、PPh3或AsPh3；
其中，式Ⅱ所示结构的配体与钼金属前体的摩尔比为1: 0.8 ~ 1.5；反应的溶剂选自乙醚、四氢呋喃、2-甲基四氢呋喃、甲苯、二甲苯、二氯甲烷、乙腈的一种或几种混合；反应温度为30 ~ 140℃。
5.一种催化剂组合物，其特征在于由活性成分和助剂组成，所述活性成分为如权利要求1所述的钳形钼配合物，所述助剂为t-BuOK、t-BuONa、i-PrONa、EtONa、MeONa、KOH、NaOH、NaHBEt3、K2CO3、Na2CO3中的一种或多种组合。
6.如权利要求5所述的催化剂组合物，其特征在于，所述助剂为NaOH和NaHBEt3，NaOH和NaHBEt3中钠与式Ⅰ所示化合物中的Mo的摩尔比为（10 ~ 500）: （0 ~ 20）: 1。
7.如权利要求5或者6所述的催化剂组合物在催化酮转移氢化成醇的反应中的应用。
8.一种醇的制备方法，其特征在于所述醇由酮在如权利要求1所述的钳形钼配合物或如权利要求5或者6所述的催化剂组合物的催化下进行转移氢化所得，反应式如下：
Figure 506909DEST_PATH_IMAGE003
R1、R2彼此独立地选自C1-6烷基、C3-15环烷基、C6-14芳基或杂芳基；反应的温度为30 ~ 110℃，反应的溶剂选自甲醇、乙醇、异丙醇、异丁醇、叔丁醇、异戊醇的一种或两种。
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CN109939737A (zh) * 2019-03-07 2019-06-28 清华大学 卡宾钴催化剂、其制备方法及其在催化氢化醛和酮化合物中的应用

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