CN112409114A - 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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CN112409114A
CN112409114A CN201910767544.3A CN201910767544A CN112409114A CN 112409114 A CN112409114 A CN 112409114A CN 201910767544 A CN201910767544 A CN 201910767544A CN 112409114 A CN112409114 A CN 112409114A
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李峰
胥婧
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，其步骤为：在反应容器中，加入酮，过渡金属催化剂，甲醇；反应混合物在水浴中加热，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。本发明用酮做原料，使用甲醇作氢源和溶剂，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）反应原子经济。

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。传统的方法中，可以使用高温高压加氢,这些方法在反应过程中存在安全隐患。
近几年来，使用甲醇作氢源来制备，甲醇是一种廉价、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、无毒的甲醇作氢源和溶剂，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，包括
Figure BDA0002172446500000011
由酮(式Ⅱ)
Figure BDA0002172446500000012
经加氢反应成目标产物的步骤。
反应是在过渡金属催化剂存在下发生，其反应通式为
Figure BDA0002172446500000021
其中，R1选自烷基、芳基、单或多取代芳基，其中，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。
本发明合成仲醇的新方法通过下述具体步骤实现：
在反应容器中，加入酮，过渡金属催化剂和甲醇；反应混合物在水浴中加热，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。
进一步的，所述的过渡金属催化剂为含有双吡啶酮配体的金属-有机双功能阴离子铱络合物，其结构如下：
Figure BDA0002172446500000022
进一步的，过渡金属催化剂用量为酮的1mol％。
进一步的，酮与甲醇的比例为1:2mmol/mL。
进一步的，反应时间不小于12小时。
进一步的，反应温度为66℃。
同现有技术相比，本发明用酮做原料，使用甲醇作氢源和溶剂，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)反应原子经济。
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 BDA0002172446500000023
将苯乙酮(120mg,1.0mmol)、cat.[Ir](5.7mg,0.01mmol,1mol％)和甲醇(2mL)依次加入到25mL克氏管中，N2保护，66℃反应12h。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：87％
1H NMR(500MHz,CDCl3)δ7.37-7.33(m,4H),7.28-7.25(m,1H),4.89(q,J＝6.3Hz,1H),1.96(br s,1H),1.49(d,J＝6.5Hz,3H)；13C NMR(125MHz,CDCl3)δ145.8,128.5,127.4,125.3,70.4,25.1.
实施例2:3-甲基苯乙醇
1-m-tolylethanol
Figure BDA0002172446500000031
将3-甲基苯乙酮(134mg,1.0mmol)、cat.[Ir](5.7mg,0.01mmol,1mol％)和甲醇(2mL)依次加入到25mL克氏管中，N2保护，66℃反应12h。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：78％
1H NMR(500MHz,CDCl3)δ7.24-7.22(m,1H),7.17(s,1H),7.15(d,J＝7.7Hz,1H),7.08(d,J＝7.5Hz,1H),4.84-4.81(m,1H),2.35(s,3H),2.03(br s,1H),1.47(d,J＝6.5Hz,3H)；13C NMR(125MHz,CDCl3)δ145.8,138.1,128.4,128.1,126.1,122.4,70.3,25.0,21.4.
实施例3:4-甲基苯乙醇
1-p-tolylethanol
Figure BDA0002172446500000032
将4-甲基苯乙酮(134mg,1.0mmol)、cat.[Ir](5.7mg,0.01mmol,1mol％)和甲醇(2mL)依次加入到25mL克氏管中，N2保护，66℃反应12h。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：84％
1H NMR(500MHz,CDCl3)δ7.25(d,J＝8.0Hz,2H),7.15(d,J＝7.8Hz,2H),4.95-4.83(m,1H),2.33(s,3H),1.95(br s,1H),1.47(d,J＝6.5Hz,3H)；13C NMR(125MHz,CDCl3)δ142.8,137.1,129.1,125.3,70.2,25.0,21.0.
实施例4:4-乙基苯乙醇
1-(4-ethylphenyl)ethanol
Figure BDA0002172446500000033
将4-乙基苯乙酮(148mg,1.0mmol)、cat.[Ir](5.7mg,0.01mmol,1mol％)和甲醇(2mL)依次加入到25mL克氏管中，N2保护，66℃反应12h。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：81％
1H NMR(500MHz,CDCl3)δ7.30(d,J＝8.0Hz,2H),7.19(d,J＝8.0Hz,2H),4.88-4.86(m,1H),2.65(q,J＝7.6Hz,2H),1.79(br s,1H),1.49(d,J＝6.5Hz,3H),1.23(t,J＝7.6Hz,3H)；13C NMR(125MHz,CDCl3)δ143.6,143.1,128.0,125.4,70.3,28.5,25.0,15.6.
实施例5:3-甲氧基苯乙醇
1-(3-Methoxyphenyl)ethanol
Figure BDA0002172446500000041
将3-甲氧基苯乙酮(150mg,1.0mmol)、cat.[Ir](5.7mg,0.01mmol,1mol％)和甲醇(2mL)依次加入到25mL克氏管中，N2保护，66℃反应12h。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)δ7.26(t,J＝5.7Hz,1H),6.95-6.93(m,1H),6.82(dd,J＝8.3Hz and 2.5Hz,1H),4.89-4.87(m,1H),3.82(s,3H),1.86(br s,1H),1.50(d,J＝6.5Hz,3H)；13C NMR(125MHz,CDCl3)δ159.7,147.6,129.4,117.6,112.8,110.9,70.2,55.1,25.1.
实施例6:3-氟苯乙醇
1-(3-Fluorophenyl)ethanol
Figure BDA0002172446500000042
将3-氟苯乙酮(138mg,1.0mmol)、cat.[Ir](5.7mg,0.01mmol,1mol％)和甲醇(2mL)依次加入到25mL克氏管中，N2保护，66℃反应12h。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)δ7.29(q,J＝7.9Hz,1H),7.13-7.08(m,2H),6.95(td,J＝8.4and 2.3Hz,1H),4.91-4.86(m,1H),2.02(br s,1H),1.48(d,J＝6.5Hz,3H)；13C NMR(125MHz,CDCl3)δ164.0(d,JC-F＝244.5Hz),148.5(d,J＝6.4Hz),130.0(d,J＝8.1Hz),120.9,114.3(d,J＝21.1Hz),112.4(d,J＝21.7Hz).
实施例7:4-氟苯乙醇
1-(4-fluorophenyl)ethanol
Figure BDA0002172446500000043
将4-氟苯乙酮(138mg,1.0mmol)、cat.[Ir](5.7mg,0.01mmol,1mol％)和甲醇(2mL)依次加入到25mL克氏管中，N2保护，66℃反应12h。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：90％
1H NMR(500MHz,CDCl3)δ7.33-7.31(m,2H),7.03-7.00(m,2H),4.87-4.86(m,1H),2.09(br s,1H),1.47(d,J＝6.5Hz,3H)；13C NMR(125MHz,CDCl3)δ163.0(d,JC-F＝243.8Hz),141.5,127.0(d,J＝8.0Hz),115.3(d,JC-F＝21.1Hz),69.7,25.2.
实施例8:4-氯苯乙醇
1-(4-chlorophenyl)ethanol
Figure BDA0002172446500000051
将4-氯苯乙酮(155mg,1.0mmol)、cat.[Ir](5.7mg,0.01mmol,1mol％)和甲醇(2mL)依次加入到25mL克氏管中，N2保护，66℃反应12h。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)δ7.32-7.29(m,4H),4.90-4.85(m,1H),1.93(br s,1H),1.47(d,J＝6.4Hz,3H)；13C NMR(125MHz,CDCl3)δ144.2,133.1,128.6,126.8,68.7,25.2.
实施例9:2,4-二氯苯乙醇
1-(2,4-Dichlorophenyl)ethanol
Figure BDA0002172446500000052
将2,4-二氯苯乙酮(189mg,1.0mmol)、cat.[Ir](5.7mg,0.01mmol,1mol％)和甲醇(2mL)依次加入到25mL克氏管中，N2保护，66℃反应12h。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)δ7.54(d,J＝8.4Hz,1H),7.34(d,J＝2.0Hz,1H),7.28-7.26(m,1H),5.24-5.22(m,1H),2.10(br s,1H),1.46(d,J＝6.4Hz,3H)；13C NMR(125MHz,CDCl3)δ141.7,133.4,132.1,129.1,127.5,127.4,66.6,23.6.
实施例10:3-溴苯乙醇
1-(3-bromophenyl)ethanol
Figure BDA0002172446500000053
将3-溴苯乙酮(199mg,1.0mmol)、cat.[Ir](5.7mg,0.01mmol,1mol％)和甲醇(2mL)依次加入到25mL克氏管中，N2保护，66℃反应12h。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：88％
1H NMR(500MHz,CDCl3)δ7.53(s,1H),7.40(d,J＝7.9Hz,1H),7.29(d,J＝7.7Hz,1H),7.21(t,J＝7.8Hz,1H),4.87-4.85(m,1H),1.95(br s,1H),1.48(dd,J＝6.5and1.5Hz,3H)；13C NMR(125MHz,CDCl3)δ148.1,130.5,130.1,128.6,124.0,122.6,69.7,25.2.
实施例11:4-溴苯乙醇
1-(4-bromophenyl)ethanol
Figure BDA0002172446500000061
将4-溴苯乙酮(199mg,1.0mmol)、cat.[Ir](5.7mg,0.01mmol,1mol％)和甲醇(2mL)依次加入到25mL克氏管中，N2保护，66℃反应12h。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)δ7.47(d,J＝8.4Hz,2H),7.24(d,J＝8.3Hz,2H),4.86-4.84(m,1H),2.0(br s,1H),1.46(d,J＝6.5Hz,3H)；13C NMR(125MHz,CDCl3)δ144.7,131.5,1127.1,121.1,69.7,25.2.
实施例12:4-三氟甲基苯乙醇
Figure BDA0002172446500000062
将4-三氟甲基苯乙酮(188mg,1.0mmol)、cat.[Ir](5.7mg,0.01mmol,1mol％)和甲醇(2mL)依次加入到25mL克氏管中，N2保护，66℃反应12h。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：90％
1H NMR(500MHz,CDCl3)δ7.59(d,J＝6.7Hz,2H),7.45(d,J＝8.2Hz,2H),4.92(q,J＝6.5Hz,1H),2.51(br s,1H),1.47(d,J＝6.5Hz,3H)；13C NMR(125MHz,CDCl3)δ149.7,129.7(q,JC-F＝32.2Hz),125.6,125.4,123.1(q,JC-F＝270.3Hz),69.7,25.2.
实施例13:4-硝基苯乙醇
1-(4-nitrophenyl)ethanol
Figure BDA0002172446500000063
将4-硝基苯乙酮(165mg,1.0mmol)、cat.[Ir](5.7mg,0.01mmol,1mol％)和甲醇(2mL)依次加入到25mL克氏管中，N2保护，66℃反应12h。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)δ8.21(d,J＝8.6Hz,2H),7.56(d,J＝8.6Hz,2H),5.04-5.02(m.1H),2.08(br s,1H),1.53(d,J＝6.6Hz,3H)；13C NMR(125MHz,CDCl3)δ153.0,147.2,126.1,123.7,69.5,25.5.
实施例14:4-氰基苯乙醇
4-(1-hydroxyethyl)benzonitrile
Figure BDA0002172446500000071
将4-氰基苯乙酮(145mg,1.0mmol)、cat.[Ir](5.7mg,0.01mmol,1mol％)和甲醇(2mL)依次加入到25mL克氏管中，N2保护，66℃反应12h。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)δ7.64(d,J＝8.2Hz,2H),7.50(d,J＝8.2Hz,2H),4.97-4.95(m,1H),2.17(br s,1H),1.50(d,J＝6.6Hz,3H)；13C NMR(125MHz,CDCl3)δ151.1,132.3,126.0,118.8,111.0,69.6,25.4.
实施例15:甲基4-(1-羟乙基)苯甲酸
Methyl 4-(1-hydroxyethyl)benzoate
Figure BDA0002172446500000072
将4-乙酰基苯甲酸甲酯(178mg,1.0mmol)、cat.[Ir](5.7mg,0.01mmol,1mol％)和甲醇(2mL)依次加入到25mL克氏管中，N2保护，66℃反应12h。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)δ7.95(d,J＝8.3Hz,2H),7.39(d,J＝8.2Hz,2H),4.90(q,J＝5.9Hz,1H),3.88(s,3H),2.91(brs,1H),1.46(d,J＝6.5Hz,3H)；13C NMR(125MHz,CDCl3)δ167.0,151.0,129.7,128.8,125.2,69.7,52.0,25.1.
实施例16:2-(1-羟乙基)吡啶
1-(pyridin-2-yl)ethanol
Figure BDA0002172446500000073
将2-乙酰基吡啶(121mg,1.0mmol)、cat.[Ir](5.7mg,0.01mmol,1mol％)和甲醇(2mL)依次加入到25mL克氏管中，N2保护，66℃反应12h。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)δ8.51(d,J＝4.1Hz,1H),7.68(td,J＝7.6and 1.5Hz,1H),7.32(d,J＝8.1Hz,1H),7.19-7.16(m,1H),4.92-4.87(m,1H),4.63(br s,1H),1.51(d,J＝6.9Hz,3H)；13C NMR(125MHz,CDCl3)δ163.3,148.0,136.7,122.1,119.7,68.9,24.1.
实施例17:2-萘乙醇
1-(naphthalen-2-yl)ethanol
Figure BDA0002172446500000081
将2-萘乙酮(170mg,1.0mmol)、cat.[Ir](5.7mg,0.01mmol,1mol％)和甲醇(2mL)依次加入到25mL克氏管中，N2保护，66℃反应12h。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：90％
1H NMR(500MHz,CDCl3)δ7.85-7.81(m,4H),7.51-7.46(m,3H),5.10-5.06(m,1H),1.91(br s,1H),1.59(d,J＝6.5Hz,3H)；13C NMR(125MHz,CDCl3)δ143.2,13.3,132.9,128.3,127.9,127.6,126.1,125.8,123.8,70.5,25.1.
实施例18:1-苯丙醇
1-phenylpropan-1-ol
Figure BDA0002172446500000082
将1-苯丙酮(134mg,1.0mmol)、cat.[Ir](5.7mg,0.01mmol,1mol％)和甲醇(2mL)依次加入到25mL克氏管中，N2保护，66℃反应12h。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：88％
1H NMR(500MHz,CDCl3)δ7.35-7.34(m,4H),7.29-7.26(m,1H),4.61-4.68(m,1H),1.90(br s,1H),1.85-1.72(m,2H),0.91(t,J＝7.4Hz,3H)；13C NMR(125MHz,CDCl3)δ144.6,128.4,127.5,125.9,76.0,31.9,10.1.
实施例19:1-苯丁醇
1-phenylbutan-1-ol
Figure BDA0002172446500000083
将1-苯丁酮(148mg,1.0mmol)、cat.[Ir](5.7mg,0.01mmol,1mol％)和甲醇(2mL)依次加入到25mL克氏管中，N2保护，66℃反应12h。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：87％
1H NMR(500MHz,CDCl3)δ7.34-7.33(m,4H),7.28-7.25(m,1H),4.67(t,J＝6.7Hz,1H),1.91(br s,1H),1.82-1.75(m,1H),1.71-1.64(m,1H),1.47-1.39(m,1H),1.35-1.25(m,1H),0.93(t,J＝7.4Hz,3H)；13C NMR(125MHz,CDCl3)δ144.9,128.4,127.4,125.9,74.4,41.2,19.0,13.9.
实施例20:二苯甲醇
Diphenylmethanol
Figure BDA0002172446500000091
将二苯甲酮(182mg,1.0mmol)、cat.[Ir](5.7mg,0.01mmol,1mol％)和甲醇(2mL)依次加入到25mL克氏管中，N2保护，66℃反应12h。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)δ7.38-7.31(m,8H),7.27-7.24(m,2H),5.83(s,1H),2.24(br s,1H)；13C NMR(125MHz,CDCl3)δ143.8,128.5,127.6,126.5,76.3.
实施例21:2-十二烷醇
dodecan-2-ol
Figure BDA0002172446500000092
将2-十二烷酮(184mg,1.0mmol)、cat.[Ir](5.7mg,0.01mmol,1mol％)和甲醇(2mL)依次加入到25mL克氏管中，N2保护，66℃反应12h。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：78％
1H NMR(500MHz,CDCl3)δ3.82-3.76(m,1H),1.46-1.40(m,4H),1.31-1.26(m,15H),1.19(d,J＝6.2Hz,3H),0.88(t,J＝6.9Hz,3H)；13C NMR(125MHz,CDCl3)δ68.2,39.4,31.9,29.6,29.6,29.3,25.8,23.5,22.7,14.1.
实施例22:环己醇
Cyclohexanol
Figure BDA0002172446500000093
将环己酮(98mg,1.0mmol)、cat.[Ir](5.7mg,0.01mmol,1mol％)和甲醇(2mL)依次加入到25mL克氏管中，N2保护，66℃反应12h。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：80％
1H NMR(500MHz,CDCl3)δ3.57(m,1H),3.20(br s,1H),1.89(s,2H),1.72(s,2H),1.54(m,1H),1.24(m,4H),1.16(m,1H)；13C NMR(125MHz,CDCl3)δ69.9,35.2,25.3,24.0.
实施例23:1,3-二苯基丙-1-醇
1,3-Diphenylpropan-1-ol
Figure BDA0002172446500000101
将3-苯基苄基酮(210mg,1.0mmol)、cat.[Ir](5.7mg,0.01mmol,1mol％)和甲醇(2mL)依次加入到25mL克氏管中，N2保护，66℃反应12h。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：83％
1H NMR(500MHz,CDCl3)δ7.35-7.34(m,4H),7.28-7.24(m,3H),7.19-7.16(m,3H),4.69-4.66(m,1H),2.77-2.63(m,2H),2.16-2.00(m,2H),1.92(br s,1H)；13C NMR(125MHz,CDCl3)δ144.6,141.8,128.5,128.4,128.4,127.6,125.9,125.8,73.9,40.5,32.0.
实施例24:4-苯基-2-丁醇
4-phenylbutan-2-ol
Figure BDA0002172446500000102
将4-苯基-2-丁酮(148mg,1.0mmol)、cat.[Ir](5.7mg,0.01mmol,1mol％)和甲醇(2mL)依次加入到25mL克氏管中，N2保护，66℃反应12h。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：80％
1H NMR(500MHz,CDCl3)δ7.29-7.26(m,2H),7.20-7.16(m,3H),3.85-3.79(m,1H),2.78-2.63(m,2H),1.81-1.71(m,2H),1.57(br s,1H),1.23(d,J＝6.2Hz,3H)；13C NMR(125MHz,CDCl3)δ142.0,128.3,125.8,67.4,40.8,32.1,23.5.。

Claims (8)

1.一种合成仲醇的方法，其特征在于，包括
Figure 955136DEST_PATH_IMAGE002
由酮Ⅱ
Figure 75538DEST_PATH_IMAGE004
在过渡金属催化剂存在下，经加氢反应生成目标产物I的步骤，
其中，R1选自烷基、芳基、单或多取代芳基；
R2选自甲基、乙基或C9烷基，苯基、苯甲基。
2.如权利要求1所述的方法，其特征在于，单或多取代芳基包括甲基苯基、甲氧基苯基、三氟甲基苯基、卤代苯基中任意一基团。
3.如权利要求1所述的方法，其特征在于，催化剂为铱络合物，其结构如下：
Figure 58538DEST_PATH_IMAGE006
。
4. 如权利要求1所述的方法，其特征在于，催化剂用量相对于酮为1 mol%。
5.如权利要求1所述的方法，其特征在于，所述的加氢反应以甲醇作为氢源。
6. 如权利要求5所述的方法，其特征在于，酮与甲醇的比例为1:2 mmol/mL。
7.如权利要求1所述的方法，其特征在于，反应在66±2℃下进行。
8.如权利要求1所述的方法，其特征在于，反应时间不小于12小时。
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