CN109384644A - 一种合成伯醇的方法 - Google Patents

一种合成伯醇的方法 Download PDF

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CN109384644A
CN109384644A CN201710683922.0A CN201710683922A CN109384644A CN 109384644 A CN109384644 A CN 109384644A CN 201710683922 A CN201710683922 A CN 201710683922A CN 109384644 A CN109384644 A CN 109384644A
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李峰
王荣周
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Nanjing University of Science and Technology
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    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
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    • C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C37/001—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by modification in a side chain
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
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    • 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
    • C07D213/24—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 substituted hydrocarbon radicals attached to ring carbon atoms
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Abstract

本发明公开了一种合成伯醇的方法，利用过渡金属催化,使用异丙醇作氢源来合成伯醇，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

一种合成伯醇的方法
技术领域
本发明属有机合成化学技术领域，具体涉及一种合成伯醇的方法。
背景技术
伯醇是一类重要的有机化合物，不仅是重要的药物中间体，而且在香料、食品等方面应用十分广泛。(a)C.I.Herrerias,X.Q.Yao,Z.P.Li,C.J.Li,Chem.Rev.2007,107,2546-2562；(b)X.F.Wu,J.L.Xiao,Chem.Commun.2007,2449-2466；(c)C.J.Li,Chem.Rev.2005,105,3095–3165；(d)M.C.Pirrung,Chem.Eur.J.2006,12,1312–1317；(e)F.Joo,Acc.Chem.Res.2002,35,738–745；(f)S.Kobayashi,K.Manabe,Acc.Chem.Res.2002,35,209–217
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伯醇，这些方法存在安全隐患，以及产生大量的废料，对环境造成一定的污染。(a)Talouki,S.A.；Grivani,G.；Croche,P.；Cadierno,V.Inorganica Chimica Acta2017,456,142-148；(b)Wang,Z.；Chen,X.；Liu,B.；Liu,Q.；Solan,G.A.；Yang,X.；Sun,W.Catal.Sci.Technol.2017,7,1297-1304；(c)Wang,F.；Tan,X.；Lv,H.；Zhang,X.Chem.Asian J.2016,11,2103-2106；(d)Du,J.；Xu.；Lin,H.；Wang,G.；Tao,M.；Zhang,W.Green Chem.2016,18,2726-2735.
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)Iturmendi,A.；García,N.；Jaseer,E.A.；Munárriz,J,；Miguel,P.J.S.；Polo,V.；Iglesias,M.；Oro,L.A.Dalton Trans.,2016,45,12835-12845；(b)Rojo,M.V.；Guetzoyana,L.；BaxendaleaI.R.Org.Biomol.Chem.2015,13,1768-1777；(c)Dutta,J.；Richmond,M.G.；Bhattacharya,S.Eur.J.Inorg.Chem.2014,4600-4610.
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，反应中无需使用碱，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伯醇的方法。
本发明通过下述技术方案实现：合成伯醇(式Ⅰ)的方法，
由醛(式Ⅱ)
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
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。
本发明合成伯醇的新方法通过下述具体步骤实现：
在反应容器中，加入醛、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，铱的络合物结构如下：
进一步地，所述反应中，铱的络合物用量为醛的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，本发明用醛做原料，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，反应原子经济性高；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:苯甲醇
Phenylmethanol
将苯甲醛(106mg,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)δ7.36-7.32(m,4H),7.29-7.23(m,1H),4.63(d,J＝2.3Hz,2H),2.40(br s,1H)；13C NMR(125MHz,CDCl3)δ140.8,128.5,127.5,126.9,65.2.
实施例2:邻甲基苯甲醇
O-tolylmethanol
将邻甲基苯甲醛(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：93％
1H NMR(500MHz,CDCl3)δ7.32-7.31(m,1H),7.22-7.14(m,3H),4.63(d,J＝2.5Hz,2H),2.60(br s,1H),2.32(s,3H)；13C NMR(125MHz,CDCl3)δ138.6,136.0,130.2,127.7,127.5,126.0,63.3,18.5.
实施例3:间甲基苯甲醇
M-tolylmethanol
将间甲基苯甲醛(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)δ7.25-7.24(m,1H),7.19(s,1H),7.16(d,J＝7.6Hz,1H),7.12(d,J＝7.5Hz,1H),4.65(s,2H),2.36(s,3H),1.73(br s,1H)；13C NMR(125MHz,CDCl3)δ140.7,138.0,128.3,128.2,127.6,123.9,65.0,21.3.
实施例4:3,4-二甲基苯甲醇
(3,4-Dimethylphenyl)methanol
将3,4-二甲基苯甲醛(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：94％
1H NMR(500MHz,CDCl3)δ7.15-7.12(m,2H),7.10(d,J＝7.7Hz,1H),4.62(s,2H),2.27(s,3H),2.26(s,3H),1.66(br s,1H)；13C NMR(125MHz,CDCl3)δ138.4,136.8,136.0,129.8,128.5,124.6,65.2,19.7,19.5.
实施例5:4-异丙基苯甲醇
(4-Isopropylphenyl)methanol
将4-异丙基苯甲醛(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：96％
1H NMR(500MHz,CDCl3)δ7.28(d,J＝8.1Hz,2H),7.22(d,J＝8.1Hz,2H),4.62(s,2H),2.95-2.86(m,1H),2.12(br s,1H),1.25(d,J＝7.0Hz,6H)；13C NMR(125MHz,CDCl3)δ148.4,138.3,127.1,126.6,65.1,33.8,24.0.
实施例6:4-甲氧基苯甲醇
(4-Methoxyphenyl)methanol
将4-甲氧基苯甲醛(136mg,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)δ7.30(d,J＝8.6Hz,2H),6.90(d,J＝8.6Hz,2H),4.61(s,2H),3.81(s,3H),1.70(br s,1H)；13C NMR(125MHz,CDCl3)δ159.1,133.1,128.6,113.9,64.9,55.2.
实施例7:3,4-二甲氧基苯甲醇
(3,4-Dimethoxyphenyl)methanol
将3,4-二甲氧基苯甲醛(166mg,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)δ6.93(s,1H),6.90(d,J＝8.1Hz,1H),6.85(d,J＝8.1Hz,1H),4,62(s,2H),3.89(s,3H),3.88(s,3H),1.77(br s,1H)；13C NMR(125MHz,CDCl3)δ148.8,148.3,133.5,119.2,110.9,110.3,64.9,55.7,55.6.
实施例8:4-氟苯甲醇
(4-Fluorophenyl)methanol
将4-氟苯甲醛(124mg,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)δ7.32-7.30(m,2H),7.05-7.01(m,2H),4.63(s,2H),2.20(br s,1H)；13C NMR(125MHz,CDCl3)δ163.2(d,JC-F＝244.1Hz),136.5,128.7(d,JC-F＝8.0Hz),115.4(d,JC-F＝21.3Hz),64.5.
实施例9:2-氯苯甲醇
将2-氯苯甲醛(141mg,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)δ7.49(d,J＝7.4Hz,1H),7.38(d,J＝7.7Hz,1H),7.31-7.23(m,2H),4.79(s,2H),2.15(br s,1H)；13C NMR(125MHz,CDCl3)δ138.1,132.7,129.3,128.8,128.7,127.0,62.8.
实施例10:4-氯苯甲醇
(4-Chlorophenyl)methanol
将4-氯苯甲醛(141mg,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)δ7.31-7.29(m,2H),7.25-7.23(m,2H),4.60(d,J＝3.6Hz,2H),2.37(br s,1H)；13C NMR(125MHz,CDCl3)δ139.2,133.3,128.6,128.2,64.4.
实施例11:3-溴苯甲醇
(3-Bromophenyl)methanol
将3-溴苯甲醛(185mg,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)δ7.51(s,1H),7.42(d,J＝7.8Hz,1H),7.27-7.20(m,2H),4.64(s,2H),2.09(br s,1H)；13C NMR(125MHz,CDCl3)δ143.0,130.6,130.1,129.8,125.3,122.6,64.4.
实施例12:4-溴苯甲醇
(4-Bromophenyl)methanol
将4-溴苯甲醛(185mg,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)δ7.49(d,J＝8.3Hz,2H),7.24(d,J＝8.3Hz,2H),4.65(s,2H),1.80(br s,1H)；13C NMR(125MHz,CDCl3)δ139.7,131.5,128.5,121.3,64.4.
实施例13:4-(二甲氨基)苯甲醇
(4-(Dimethylamino)phenyl)methanol
将4-(二甲氨基)苯甲醛(151mg,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：89％
1H NMR(500MHz,CDCl3)δ7.23(d,J＝8.5Hz,2H),6.72(d,J＝8.5Hz,2H),4.53(s,2H),2.93(s,6H),1.90(br s,1H)；13C NMR(125MHz,CDCl3)δ150.3,128.9,128.5,112.6,65.2,40.6.
实施例14:4-羟基苯甲醇
4-(Hydroxymethyl)phenol
将4-羟基苯甲醛(122mg,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,[D6]DMSO)δ9.23(s,1H),7.11(d,J＝8.3Hz,2H),6.71(d,J＝8.3Hz,2H),4.94(t,J＝5.7Hz,1H),4.36(d,J＝5.7Hz,2H)；13C NMR(125MHz,[D6]DMSO)δ156.2,132.8,128.1,114.8,62.8.
实施例15:2-硝基苯甲醇
(2-Nitrophenyl)methanol
将2-硝基苯甲醛(151mg,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)δ8.11(d,J＝8.2Hz,1H),7.75(d,J＝7.7Hz,1H),7.68(t,J＝7.5Hz,1H),7.48(t,J＝7.8Hz,1H),4.98(s,2H),2.60(br s,1H)；13C NMR(125MHz,CDCl3)δ147.5,136.8,134.1,129.8,128.4,124.9,62.4.
实施例16:4-三氟甲氧基苯甲醇
(4-(Trifluoromethoxy)phenyl)methanol
将4-三氟甲氧基苯甲醛(190mg,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：88％
1H NMR(500MHz,CDCl3)δ7.39(d,J＝7.9Hz,2H),7.21(d,J＝8.1Hz,2H),4.69(d,J＝6.8Hz,2H),2,21(br s,1H)；13C NMR(125MHz,CDCl3)δ148.6,139.4,128.3,121.5(q,JC-F＝255.5Hz),121.0,64.4.
实施例17:1-萘甲醇
Naphthalen-1-ylmethanol
将1-萘甲醛(158mg,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)δ8.15(d,J＝8.4Hz,1H),7.89(d,J＝7.8Hz,1H),7.83(d,J＝8.2Hz,1H),7.57-7.50(m,3H),7.45(t,J＝7.6Hz,1H),5.17(s,2H),1.74(br s,1H)；13CNMR(125MHz,CDCl3)δ136.2,133.7,131.1,128.6,128.4,126.2,125.8,125.3,125.2,123.6,63.4.
实施例18:吡啶-2-甲醇
Pyridin-2-ylmethanol
将吡啶-2-甲醛(107mg,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：83％
1H NMR(500MHz,CDCl3)δ8.51(d,J＝4.8Hz,1H),7.69-7.66(td,J＝7.7and 1.7Hz,1H),7.33(d,J＝7.8Hz,1H),7.20-7.17(m,1H),4.76(s,2H),4.56(br s,1H)；13C NMR(125MHz,CDCl3)δ159.6,148.4,136.7,122.2,120.7,64.2.
实施例19:3-苯丙醇
3-Phenylpropan-1-ol
将3-苯丙醛(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，120℃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)δ7.29-7.27(m,2H),7.20-7.17(m,3H),3.66(t,J＝6.5Hz,2H),2.70(t,J＝7.8Hz,2H),2.39(br s,1H),1.91-1.86(m,2H)；13C NMR(125MHz,CDCl3)δ141.8,128.4,128.3,125.8,62.2,34.1,32.0.
实施例20:正辛醇
Octan-1-ol
将正辛醛(128mg,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，120℃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)δ3.64(t,J＝6.7Hz,2H),2.45(br s,1H),1.59-1.54(m,2H),1.36-1.23(m,10H),0.88(t,J＝6.9Hz,3H)；13C NMR(125MHz,CDCl3)δ63.0,32.7,31.8,29.4,29.2,25.7,22.6,14.0.
实施例21:环己烷基甲醇
Cyclohexylmethanol
将环己烷基甲醛(112mg,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，120℃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：91％
1H NMR(500 MHz,CDCl3)δ3.43(d,J＝6.4 Hz,2H),2.08(br s,1H),1.76-1.66(m,5H),1.51-1.44(m,1H),1.30-1.12(m,3H),0.97-0.89(m,2H)；13C NMR(125 MHz,CDCl3)δ68.6,40.4,29.5,26.5,25.8.。

Claims (6)

1.合成伯醇Ⅰ的方法，其特征在于，
R1-OH
I
由醛Ⅱ在过渡金属催化剂存在下，
R1＝O
II
经加氢反应得到所述目标产物，
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。
2.如权利要求1所述的方法，其特征在于，反应在溶剂异丙醇存在下进行。
3.如权利要求1所述的方法，其特征在于，过渡金属催化剂为铱的络合物，其结构如下：
4.如权利要求1所述的方法，其特征在于，过渡金属催化剂用量为醛的0.2mol％。
5.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。
6.如权利要求1所述的方法，其特征在于，反应温度为82-120℃。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112409114A (zh) * 2019-08-20 2021-02-26 南京理工大学 一种合成仲醇的方法
CN113105299A (zh) * 2021-04-08 2021-07-13 上海橡实化学有限公司 一种在水相中合成伯醇的方法

Citations (1)

* Cited by examiner, † Cited by third party
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

Patent Citations (1)

* Cited by examiner, † Cited by third party
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

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
JOHN R. MIECZNIKOWSKI 等: "Hydrogen Transfer Reduction of Aldehydes with Alkali-Metal Carbonates and Iridium NHC Complexes", 《ORGANOMETALLICS》 *
RICARDO CASTARLENAS 等: "Preparation, X-ray Structure, and Reactivity of an Osmium-Hydroxo Complex Stabilized by an N-Heterocyclic Carbene Ligand: A Base-Free Catalytic Precursor for Hydrogen Transfer from 2-Propanol to Aldehydes", 《ORGANOMETALLICS》 *
RYOKO KAWAHARA 等: "Cooperative Catalysis by Iridium Complexes with a Bipyridonate Ligand: Versatile Dehydrogenative Oxidation of Alcohols and Reversible Dehydrogenation–Hydrogenation between 2-Propanol and Acetone", 《ANGEW.CHEM.INT.ED.》 *
STEPHANIE J. LUCAS 等: "A robust method to heterogenise and recycle group 9 catalysts", 《CHEMCOMM》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112409114A (zh) * 2019-08-20 2021-02-26 南京理工大学 一种合成仲醇的方法
CN113105299A (zh) * 2021-04-08 2021-07-13 上海橡实化学有限公司 一种在水相中合成伯醇的方法
CN113105299B (zh) * 2021-04-08 2022-03-18 上海橡实化学有限公司 一种在水相中合成伯醇的方法

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