CN109384645B - 一种合成仲醇的方法 - Google Patents

一种合成仲醇的方法 Download PDF

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CN109384645B
CN109384645B CN201710683910.8A CN201710683910A CN109384645B CN 109384645 B CN109384645 B CN 109384645B CN 201710683910 A CN201710683910 A CN 201710683910A CN 109384645 B CN109384645 B CN 109384645B
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李峰
王荣周
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Nanjing University of Science and Technology
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Abstract

本发明公开了一种合成仲醇的方法，利用过渡金属催化，使用异丙醇作氢源来合成仲醇，该反应不仅使用廉价、环保的异丙醇作氢源和溶剂，而且具有产率高、环保等优点，因此该反应具有广阔的发展前景。

Description

一种合成仲醇的方法
技术领域
本发明属有机合成化学技术领域，具体涉及一种合成仲醇的方法。
背景技术
仲醇是一类重要的化合物，不仅是重要的有机中间体，而且在药物、农药、香料等精细化工方面应用十分广泛。(a)
Figure BDA0001376185860000012
B.Reduction Reactions with NHC-bearingComplexes.In N-Heterocyclic Carbenes:From Laboratory Curiosities to EfficientSynthetic Tools；Díez-González,S.,Ed.；(b)RSC Catalysis Series No.6,RoyalSociety of Chemistry:Cambridge,2011,pp 366-398.(c)Díez-González,S.；Marion,N.；Nolan,S.P.Chem.Rev.2009,109,3612.(d)Gladiali,S.；Alberico,E.Chem.Soc.Rev.2006,35,226.
传统的方法中，可以使用高温高压加氢，加入硼氢化钠等无机还原剂，或者使用甲酸和甲酸钠来制备仲醇，这些方法存在着反应过程存在安全隐患，以及产生大量的废料，对环境造成一定的污染。(a)
Figure BDA0001376185860000013
S.；Obenauf.J.；Kempe.R.J.Am.Chem.Soc.2015,137,7998-8001.(b)Hodgkinson,R,；Grosso,A.D.；Clarkson,G.；Wills,Martin.DaltonTrans.2016,45,3992-4005.(c)Voisine,A.B.；Wang,D.；Roisnel,T.；Darcel,C.；Sortais,J.B.Catalysis Communications.2017,92,1-4.(d)El-Asaad,B.；Guicheret,B.；Métay,Estell.；Karamé,I.；Lemaire,M.Journal of Molecular Catalysis A:Chemical.2016,411,196-202.Rayati,S.；Bohloulbandi,E.；Zakavi,S.J.Coord.Chem.2015,69,638-649.
近几年来，使用异丙醇作氢源来制备，异丙醇是一种廉价、安全、无毒的氢给体，这种方法受到了广泛的关注。但是在反应过程中需要加入强碱或者弱碱。(a)Yu,Z.；Zeng,F.；Sun,X.；Deng,H.；Dong,J.；Chen,J.；Wang,H.；Pei,C.J.Organometallic.Chem.2007,692,2306-2313.(b)Bigler,R.；Huber,R.；Mezzetti,A.Angew.Chem.Int.Ed.2015,54,1-5.Moore,C.M.；(c)Szymczak,N.K.Chem.Commun.,2013,49,400-402.(d)Sakaguchi,S.；Yamaga,T.Ishii Y.J.Org.Chem.2001,66,4710-4712.(e)Fernández,F.E.；Puerta,M.C.；Valerga,P.Organometallics 2012,31,6868-6879.(f)Li,K.；Niu,J.；Yang,M.；Li,Z.；Wu,L.；Hao,X.；Song,M.Organometallics 2015,34,1170-1176.
因此，从有机合成的角度，发展一类新的有机金属催化剂，通过使用廉价、安全、无毒的异丙醇作氢源和溶剂，反应中不需要加入碱，能够在环境友好和温和的状态下来催化这类反应有重要的意义。
发明内容
本发明的目的在于提供一种合成仲醇的方法。
本发明通过下述技术方案实现：合成仲醇(式Ⅰ)的方法，
Figure BDA0001376185860000011
由酮(式Ⅱ)在过渡金属催化剂存在下，
Figure BDA0001376185860000021
经加氢反应得到目标产物。
反应是在过渡金属催化剂存在下发生，其反应通式为
Figure BDA0001376185860000022
其中，R1选自烷基、芳基、单或多取代芳基，单或多取代芳基优选甲基苯基、甲氧基苯基、三氟甲基苯基、卤代苯基；
R2代表一个取代基，选自甲基、乙基或C9烷基，苯基、苯甲基。
本发明合成仲醇的方法通过下述具体步骤实现：
在反应容器中，加入酮，过渡金属催化剂铱的络合物和溶剂异丙醇；反应混合物在油浴中加热，反应数小时后，冷却到室温，旋转蒸发除去溶剂，然后通过柱分离，得到目标化合物。
进一步地，所述反应中，铱的络合物结构为：
Figure BDA0001376185860000023
进一步地，所述反应中，铱的络合物用量为酮的0.2mol％。
进一步地，所述反应中，反应时间不少于6小时。
进一步地，所述反应中，反应温度不低于82℃。
同现有技术相比，本发明用酮做原料，使用异丙醇作氢源和溶剂，在过渡金属催化剂的参与下，通过氢转移，生成伯醇。反应展现出三个显著的优点：1)不加碱；2)反应温度低；3)催化剂用量低，反应原子经济；所以，该反应符合绿色化学的要求，具有广阔的发展前景。
具体实施方式
展示一下实例来说明本发明的某些实施例，且不应解释为限制本发明的范围。对本发明公开的内容可以同时从材料，方法和反应条件上进行许多改进，变化和改变。所有这些改进，变化和改变均确定地落入本发明的精神和范围之内。
实施例1:1-苯乙醇
1-phenylethanol
Figure BDA0001376185860000024
将苯乙酮(120mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol％)和异丙醇(5mL)依次加入到25mL克氏管中，N2保护，82℃反应6h。冷却到室温，旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：95％
1H NMR(500MHz,CDCl3)δ7.39-7.34(m,4H),7.29-7.28(m,1H),4.93-4.89(m,1H),1.80(br s,1H),1.51(d,J＝6.5Hz,3H)；13C NMR(125MHz,CDCl3)δ145.8,128.4,127.4,125.3,70.3,25.1.
实施例2:3-甲基苯乙醇
1-m-tolylethanol
Figure BDA0001376185860000031
将3-甲基苯乙酮(134mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol％)和异丙醇(5mL)依次加入到25mL克氏管中，N2保护，82℃反应6h。冷却到室温，旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：95％
1H NMR(500MHz,CDCl3)δ7.24(t,J＝7.4Hz,1H),7.19(s,1H),7.17(d,J＝7.6Hz,1H),7.09(d,J＝7.5Hz,1H),4.87(q,J＝6.4Hz,1H),2.36(s,1H),1.82(br s,1H),1.49(d,J＝6.5Hz,3H)；13C NMR(125MHz,CDCl3)δ145.8,138.1,128.4,128.2,126.1,122.4,70.4,25.1,21.4.
实施例3:4-甲基苯乙醇
1-p-tolylethanol
Figure BDA0001376185860000032
将4-甲基苯乙酮(134mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol％)和异丙醇(5mL)依次加入到25mL克氏管中，N2保护，82℃反应6h。冷却到室温，旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：93％
1H NMR(500MHz,CDCl3)δ7.28(d,J＝8.3Hz,2H),7.17(d,J＝7.9Hz,2H),4.88(q,J＝6.4Hz,1H),3.34(s,3H),1.75(br s,1H),1.49(d,J＝6.5Hz,3H)；13C NMR(125MHz,CDCl3)δ142.8,137.0,129.1,125.3,70.1,25.0,21.0.
实施例4:4-乙基苯乙醇
1-(4-ethylphenyl)ethanol
Figure BDA0001376185860000033
将4-乙基苯乙酮(148mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol％)和异丙醇(5mL)依次加入到25mL克氏管中，N2保护，82℃反应6h。冷却到室温，旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：97％
1H NMR(500MHz,CDCl3)δ7.29(d,J＝8.1Hz,2H),7.19(d,J＝8.0Hz,2H),4.87(q,J＝6.4,Hz,1H),2.65(q,J＝7.6Hz,2H),1.88(br s,1H),1.49(d,J＝6.5Hz,3H),1.23(t,J＝5.1Hz,3H)；13C NMR(125MHz,CDCl3)δ143.5,143.1,127.9,125.4,70.2,28.5,25.0,15.6.
实施例5:4-甲氧基苯乙醇
1-(4-methoxyphenyl)ethanol
Figure BDA0001376185860000041
将4-甲氧基苯乙酮(150mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol％)和异丙醇(5mL)依次加入到25mL克氏管中，N2保护，82℃反应6h。冷却到室温，旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：86％
1H NMR(500MHz,CDCl3)δ7.31(d,J＝8.6Hz,2H),6.90(d,J＝8.7Hz,2H),4.87(q,J＝6.4Hz,1H),3.81(s,3H),1.73(br s,1H),1.49(d,J＝6.5Hz,3H)；13C NMR(125MHz,CDCl3)δ158.9,138.0,126.6,113.8,69.9,55.2,25.0.
实施例6:4-氟苯乙醇
1-(4-fluorophenyl)ethanol
Figure BDA0001376185860000042
将4-氟苯乙酮(138mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol％)和异丙醇(5mL)依次加入到25mL克氏管中，N2保护，82℃反应6h。冷却到室温，旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：96％
1H NMR(500MHz,CDCl3)δ7.34-7.32(m,2H),7.02(t,J＝8.7Hz,2H),4.88(q,J＝6.4Hz,1H),2.01(br s,1H),1.47(dd,J＝2,1and 6.5Hz,3H)；13C NMR(125MHz,CDCl3)δ163.1(d,JC-F＝243.8Hz),141.5(d,JC-F＝2.7Hz),127.1(d,JC-F＝8.0Hz),115.3,(d,JC-F＝21.3Hz),69.7,25.2.
实施例7:4-氯苯乙醇
1-(4-chlorophenyl)ethanol
Figure BDA0001376185860000051
将4-氯苯乙酮(155mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol％)和异丙醇(5mL)依次加入到25mL克氏管中，N2保护，82℃反应6h。冷却到室温，旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：95％
1H NMR(500MHz,CDCl3)δ7.32-7.28(m,4H),4.87(q,J＝6.5Hz,1H),2.04(br s,1H),1.47(d,J＝6.5Hz,3H)；13C NMR(125MHz,CDCl3)δ144.2,133.0,128.6,126.8,69.7,25.2.
实施例8:3,4-二氯苯乙醇
1-(3,4-dichlorophenyl)ethanol
Figure BDA0001376185860000052
将3,4-二氯苯乙酮(189mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol％)和异丙醇(5mL)依次加入到25mL克氏管中，N2保护，82℃反应6h。冷却到室温，旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：97％
1H NMR(500MHz,CDCl3)δ7.54(d,J＝8.4Hz,1H),7.34(d,J＝2.0Hz,1H),7.28(m,1H),5.24(q,J＝6.3Hz,1H),2.09(br s,1H),1.47(d,J＝6.5Hz,3H)；13C NMR(125MHz,CDCl3)δ141.7,133.3.132.1,129.1,127.5,127.4,66.5,23.6.
实施例9:3-溴苯乙醇
1-(3-bromophenyl)ethanol
Figure BDA0001376185860000053
将3-溴苯乙酮(199mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol％)和异丙醇(5mL)依次加入到25mL克氏管中，N2保护，82℃反应6h。冷却到室温，旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：99％
1H NMR(500MHz,CDCl3)δ7.54(d,J＝1.6Hz,1H),7.40(d,J＝7.7Hz,1H),7.29(d,J＝7.7Hz,1H),7.21(t,J＝7.7Hz,1H),4.87(q,J＝6.3Hz,1H),1.87(br s,1H),1.49(dd,J＝2.0and 6.3Hz,3H)；13C NMR(125MHz,CDCl3)δ148.1,130.5,130.1,128.6,124.0,122.6,69.8,25.2.
实施例10:4-溴苯乙醇
1-(4-bromophenyl)ethanol
Figure BDA0001376185860000061
将4-溴苯乙酮(199mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol％)和异丙醇(5mL)依次加入到25mL克氏管中，N2保护，82℃反应6h。冷却到室温，旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：98％
1H NMR(500MHz,CDCl3)δ7.47(d,J＝8.4Hz,2H),7.25(d,J＝8.4Hz,2H),4.86(q,J＝6.5Hz,1H),1.96(br s,1H),1.47(d,J＝6.5Hz,3H)；13C NMR(125MHz,CDCl3)δ144.8,131.5,127.1,121.3,69.7,25.2.
实施例11:4-硝基苯乙醇
1-(4-nitrophenyl)ethanol
Figure BDA0001376185860000062
将4-硝基苯乙酮(165mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol％)和异丙醇(5mL)依次加入到25mL克氏管中，N2保护，82℃反应6h。冷却到室温，旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：96％
1H NMR(500MHz,CDCl3)δ8.22(d,J＝8.8Hz,2H),7.56(d,J＝8.6Hz,2H),5.03(t,J＝6.5Hz,1H),2.00(br s,1H),1.53(d,J＝6.5Hz,3H)；13C NMR(125MHz,CDCl3)δ153.1,147.1,126.1,123.7,69.4,25.4.
实施例12:4-氰基苯乙醇
4-(1-hydroxyethyl)benzonitrile
Figure BDA0001376185860000063
将4-氰基苯乙酮(145mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol％)和异丙醇(5mL)依次加入到25mL克氏管中，N2保护，82℃反应6h。冷却到室温，旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：95％
1H NMR(500MHz,CDCl3)δ7.64(d,J＝7.8Hz,2H),7.50(d,J＝8.2Hz,2H),4.97(q,J＝6.4Hz,1H),2.19(br s,1H),1.50(d,J＝6.5Hz,3H)；13C NMR(125MHz,CDCl3)δ151.1,132.3,126.0,118.8,111.0,69.6,25.4.
实施例13:4-三氟甲基苯乙醇
Figure BDA0001376185860000071
将4-三氟甲基苯乙酮(188mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol％)和异丙醇(5mL)依次加入到25mL克氏管中，N2保护，82℃反应6h。冷却到室温，旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：94％
1H NMR(500MHz,CDCl3)δ7.61(d,J＝8.1Hz,2H),7.48(d,J＝8.1Hz,2H),4.96(q,J＝6.5Hz,1H),2.09(br s,1H),1.50(d,J＝6.5Hz,3H)；13C NMR(125MHz,CDCl3)δ149.7,129.7(q,JC-F＝32.1Hz),125.6,125.4(d,JC-F＝3.4Hz),125.2(q,JC-F＝270.3Hz),69.8,25.3.
实施例14:1-(2-噻吩基)乙醇
1-(thiophen-2-yl)ethanol
Figure BDA0001376185860000072
将1-(2-噻吩基)乙酮(126mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol％)和异丙醇(5mL)依次加入到25mL克氏管中，N2保护，82℃反应6h。冷却到室温，旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：91％
1H NMR(500MHz,CDCl3)δ7.24(d,J＝4.9Hz,1H),6.98-6.95(m,2H),5.15-5.11(m,1H),2.10(br s,1H),1.61(dd,J＝1.9and 6.4Hz,3H)；13C NMR(125MHz,CDCl3)δ149.8,126.6,124.3,123.1,66.1,25.2.
实施例15:2-(1-羟乙基)吡啶
1-(pyridin-2-yl)ethanol
Figure BDA0001376185860000073
将2-乙酰基吡啶(121mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol％)和异丙醇(5mL)依次加入到25mL克氏管中，N2保护，82℃反应6h。冷却到室温，旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：93％
1H NMR(500MHz,CDCl3)δ8.55(d,J＝4.9Hz,1H),7.69(td,J＝1.7and 7.7Hz,1H),7.29(d,J＝8.0Hz,1H),7.22-7.19(m,1H),4.90(q,J＝6.5Hz,1H),4.28(br s,1H),1.52(d,J＝6.6Hz,3H)；13C NMR(125MHz,CDCl3)δ163.1,148.1,136.7,122.1,119.7,68.9,24.1.
实施例16:二苯甲醇
Diphenylmethanol
Figure BDA0001376185860000081
将二苯甲酮(182mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol％)和异丙醇(5mL)依次加入到25mL克氏管中，N2保护，82℃反应6h。冷却到室温，旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：95％
1H NMR(500MHz,CDCl3)δ7.38(d,d,J＝7.3Hz,4H),7.34-7.31(m,4H),7.26(t,d,J＝7.7Hz,2H),5.83(s,1H),2.26(br s,1H)；13C NMR(125MHz,CDCl3)δ143.8,128.5,127.6,126.5,76.2.
实施例17:2-萘乙醇
1-(naphthalen-2-yl)ethanol
Figure BDA0001376185860000082
将2-萘乙酮(170mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol％)和异丙醇(5mL)依次加入到25mL克氏管中，N2保护，82℃反应6h。冷却到室温，旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：98％
1H NMR(500MHz,CDCl3)δ7.83-7.79(m,4H),7.50-7.44(m,3H),5.06(q,J＝6.4Hz,1H),1.99(br s,1H),1.58(d,J＝6.5Hz,3H)；13C NMR(125MHz,CDCl3)δ143.2,133.3,132.9,128.3,127.9,127.7,126.1,125.8,123.8,70.5,25.1.
实施例18:1-苯丙醇
1-phenylpropan-1-ol
Figure BDA0001376185860000083
将1-苯丙酮(134mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol％)和异丙醇(5mL)依次加入到25mL克氏管中，N2保护，82℃反应6h。冷却到室温，旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：92％
1H NMR(500MHz,CDCl3)δ7.35-7.33(m,4H),7.29-7.26(m,1H),4.60(t,J＝6.6Hz,1H),1.87(br s,1H),1.87-1.73(m,2H),0.92(t,J＝7.4Hz,3H)；13C NMR(125MHz,CDCl3)δ144.6,128.4,127.5,126.0,31.9,10.1.
实施例19:4-氯苯丙醇
1-(4-chlorophenyl)propan-1-ol
Figure BDA0001376185860000091
将4-氯苯丙酮(169mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol％)和异丙醇(5mL)依次加入到25mL克氏管中，N2保护，82℃反应6h。冷却到室温，旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：97％
1H NMR(500MHz,CDCl3)δ7.31-7.29(m,2H),7.27-7.25(m,2H),4.56(t,J＝5.8Hz,1H),2.06(br s,1H),1.81-1.66(m,2H),0.89(td,J＝1.3and 7.4Hz,3H)；13C NMR(125MHz,CDCl3)δ143.0,133.1,128.5,127.3,75.2,31.9,9.9.
实施例20:4-溴苯丙醇
1-(4-bromophenyl)propan-1-ol
Figure BDA0001376185860000092
将4-溴苯丙酮(213mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol％)和异丙醇(5mL)依次加入到25mL克氏管中，N2保护，82℃反应6h。冷却到室温，旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：96％
1H NMR(500MHz,CDCl3)δ7.47(d,J＝8.4Hz,2H),7.22(d,J＝8.4Hz,2H),4.57(t,J＝6.5Hz,1H),1.91(br s,1H),1.83-1.67(m,2H),0.90(t,J＝7.4Hz,3H)；13C NMR(125MHz,CDCl3)δ143.5,131.4,127.7,121.1,75.3,31.9,9.9.
实施例21:1-苯丁醇
1-phenylbutan-1-ol
Figure BDA0001376185860000093
将1-苯丁酮(148mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol％)和异丙醇(5mL)依次加入到25mL克氏管中，N2保护，82℃反应6h。冷却到室温，旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：93％
1H NMR(500MHz,CDCl3)δ7.35(d,J＝4.4Hz,4H),7.29-7.26(m,1H),4.68(t,J＝6.7Hz,1H),1.82-1.76(m,2H),1.72-1.65(m,1H),1.49-1.39(m,1H),1.36-1.26(m,1H),0.93(t,J＝7.4Hz,3H)；13C NMR(125MHz,CDCl3)δ144.9,128.4,127.5,125.9,74.4,41.2,19.0,13.9.
实施例22:4-苯基-2-丁醇
4-phenylbutan-2-ol
Figure BDA0001376185860000101
将4-苯基-2-丁酮(148mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol％)和异丙醇(5mL)依次加入到25mL克氏管中，N2保护，82℃反应6h。冷却到室温，旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：95％
1H NMR(500MHz,CDCl3)δ7.28(t,J＝7.5Hz,2H),7.21-7.17(m,3H),3.85-3.79(m,1H),2.78-2.64(m,2H),1.81-1.74(m,2H),1.53(br s,1H),1.23(d,J＝6.2Hz,3H)；13C NMR(125MHz,CDCl3)δ142.0,128.4,125.8,67.4,40.8,32.1,23.6.
实施例23:环己醇
Cyclohexanol
Figure BDA0001376185860000102
将环己酮(98mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol％)和异丙醇(5mL)依次加入到25mL克氏管中，N2保护，82℃反应6h。冷却到室温，旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：82％
1H NMR(500MHz,CDCl3)δ3.62-3.59(m,1H),1.90-1.86(m,3H),1.75-1.72(m,2H),1.57-1.53(m,1H),1.32-1.46(m,5H)；13C NMR(125MHz,CDCl3)δ70.2,35.5,25.4,24.1.
实施例24:2-十二烷醇
dodecan-2-ol
Figure BDA0001376185860000103
将2-十二烷酮(184mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol％)和异丙醇(5mL)依次加入到25mL克氏管中，N2保护，82℃反应6h。冷却到室温，旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：93％
1H NMR(500MHz,CDCl3)δ3.82-3.78(m,1H),1.46-1.27(m,19H),1.20(d,J＝6.2Hz,3H),0.89(t,J＝6.9Hz,3H)；13C NMR(125MHz,CDCl3)δ68.2,39.4,31.9,29.6,29.3,25.8,23.5,22.7,14.1.。

Claims (5)

1.合成仲醇Ⅰ的方法，其特征在于，
Figure FDA0003035354200000011
由酮Ⅱ在过渡金属催化剂存在下，
Figure FDA0003035354200000012
经加氢反应得到目标产物，
其中，R1选自烷基、芳基、甲基苯基、甲氧基苯基、三氟甲基苯基、卤代苯基；
R2代表一个取代基，选自甲基、乙基或C9烷基，苯基、苯甲基；
过渡金属催化剂为铱的络合物，其结构为：
Figure FDA0003035354200000013
2.如权利要求1所述的方法，其特征在于，铱的络合物用量为酮的0.2mol％。
3.如权利要求1所述的方法，其特征在于，反应时间不少于6小时。
4.如权利要求1所述的方法，其特征在于，反应温度82-120℃。
5.如权利要求1所述的方法，其特征在于，所述反应在溶剂异丙醇存在下进行。
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Publication number Priority date Publication date Assignee Title
CN104203892A (zh) * 2012-02-23 2014-12-10 关东化学株式会社 脱氢用催化剂、使用该催化剂的羰基化合物及氢的制造方法

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