CN109384644B - 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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CN109384644B
CN109384644B CN201710683922.0A CN201710683922A CN109384644B CN 109384644 B CN109384644 B CN 109384644B CN 201710683922 A CN201710683922 A CN 201710683922A CN 109384644 B CN109384644 B CN 109384644B
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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，
Figure BDA0001376185920000011
由醛(式Ⅱ)
Figure BDA0001376185920000012
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 BDA0001376185920000021
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：
Figure BDA0001376185920000022
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
Figure BDA0001376185920000023
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
Figure BDA0001376185920000031
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
Figure BDA0001376185920000032
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
Figure BDA0001376185920000033
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
Figure BDA0001376185920000041
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
Figure BDA0001376185920000042
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
Figure BDA0001376185920000043
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
Figure BDA0001376185920000044
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
Figure BDA0001376185920000051
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
Figure BDA0001376185920000052
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
Figure BDA0001376185920000053
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
Figure BDA0001376185920000061
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
Figure BDA0001376185920000062
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
Figure BDA0001376185920000063
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
Figure BDA0001376185920000071
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
Figure BDA0001376185920000072
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
Figure BDA0001376185920000073
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
Figure BDA0001376185920000081
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
Figure BDA0001376185920000082
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
Figure BDA0001376185920000083
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
Figure BDA0001376185920000084
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 (5)

1.合成伯醇Ⅰ的方法，其特征在于，
Figure DEST_PATH_IMAGE002
由醛Ⅱ在过渡金属催化剂存在下，
Figure DEST_PATH_IMAGE004
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；
过渡金属催化剂为铱的络合物，其结构如下：
Figure DEST_PATH_IMAGE006
。
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，过渡金属催化剂用量为醛的0.2 mol%。
4.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。
5.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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