CN110015947B - 一种合成不饱和伯醇的方法 - Google Patents

一种合成不饱和伯醇的方法 Download PDF

Info

Publication number
CN110015947B
CN110015947B CN201810017911.3A CN201810017911A CN110015947B CN 110015947 B CN110015947 B CN 110015947B CN 201810017911 A CN201810017911 A CN 201810017911A CN 110015947 B CN110015947 B CN 110015947B
Authority
CN
China
Prior art keywords
reaction
isopropanol
solvent
cdcl
nmr
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201810017911.3A
Other languages
English (en)
Other versions
CN110015947A (zh
Inventor
李峰
王荣周
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanjing University of Science and Technology
Original Assignee
Nanjing University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanjing University of Science and Technology filed Critical Nanjing University of Science and Technology
Priority to CN201810017911.3A priority Critical patent/CN110015947B/zh
Publication of CN110015947A publication Critical patent/CN110015947A/zh
Application granted granted Critical
Publication of CN110015947B publication Critical patent/CN110015947B/zh
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06Preparation of nitro compounds
    • C07C201/12Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132Preparation 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
    • C07C29/136Preparation 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
    • C07C29/14Preparation 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 a —CHO group
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01Preparation of ethers
    • C07C41/18Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/26Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D307/00Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40Radicals substituted by oxygen atoms
    • C07D307/42Singly bound oxygen atoms

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本发明公开了一种合成不饱和伯醇的方法,在反应容器中,加入不饱和醛、过渡金属催化剂铱络合物和异丙醇;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。本发明用不饱和醛做原料,使用异丙醇作氢源和溶剂,在过渡金属铱催化剂的参与下,通过氢转移,生成不饱和伯醇。反应展现出三个显著的优点:1)反应温度低;2)使用廉价、安全、无毒的异丙醇;3)催化剂用量低,反应原子经济性高;4)选择性好。所以,该反应符合绿色化学的要求,具有广阔的发展前景。

Description

一种合成不饱和伯醇的方法
技术领域
本发明属有机合成化学技术领域,具体涉及一种合成不饱和伯醇的方法。
背景技术
不饱和伯醇是一类重要的有机化合物,不仅是重要的药物中间体,而且广泛的应用在香料、食品等方面。(a)M.C.Pirrung,Chem.Eur.J.2006,12,1312–1317;(b)S.Kobayashi,K.Manabe,Acc.Chem.Res.2002,35,209-217;(c)C.I.Herrerias,X.Q.Yao,Z.P.Li,C.J.Li,Chem.Rev.2007,107,2546-2562;(d)F.Joo,Acc.Chem.Res.2002,35,738–745;(e)X.F.Wu,J.L.Xiao,Chem.Commun.2007,2449-2466;
传统的方法中,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不饱和伯醇,这些方法存在安全隐患,选择性差以及产生大量的废料等问题,对环境也造成一定的污染。(a)Talouki,S.A.;Grivani,G.;Croche,P.;Cadierno,V.Inorganica Chimica Acta 2017,456,142-148;(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,开始使用异丙醇作氢源来制备不饱和伯醇,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少量的强碱或者弱碱。(a)Talwar,D.;Wu,X.;Saidi,O.;Salguero,N.P.;Xiao,J.Chem.Eur.J.2014,20,12835-12842;(b)Rojo,M.V.;Guetzoyana,L.;Baxendalea I.R.Org.Biomol.Chem.2015,13,1768-1777;(c)Fleischer,S.;Zhou,S.;Junge,K.;Beller,Matthias.Angew.Chem.Int.Ed.2013,52,5120-5124;(d)Malacea,R.;Poli,R.;Manoury,E.Coord.Chem.Rev.2010,254,729-752;(e)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.
因此,从有机反应的角度出发,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不饱和伯醇的方法。
本发明通过下述技术方案实现:合成不饱和伯醇(式Ⅰ)
Figure BDA0001542547770000011
由不饱和醛(式Ⅱ)
Figure BDA0001542547770000012
经加氢生成目标产物
反应是在过渡金属铱催化剂存在下发生,其反应通式为
Figure BDA0001542547770000021
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、硝基苯基、卤代苯基;R2选自甲基、乙基、戊基、己基。
本发明合成不饱和伯醇的新方法通过下述具体步骤实现:
在反应容器中,加入不饱和醛、过渡金属催化剂铱络合物和异丙醇;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。
步骤中所述的金属铱络合物为
Figure BDA0001542547770000022
进一步的,金属铱络合物用量为不饱和醛的0.2mol%。
进一步的,反应时间不少于6小时。
进一步的,反应温度不低于82℃。
同现有技术相比,本发明用不饱和醛做原料,使用异丙醇作氢源和溶剂,在过渡金属铱催化剂的参与下,通过氢转移,生成不饱和伯醇。反应展现出三个显著的优点:1)反应温度低;2)使用廉价、安全、无毒的异丙醇;3)催化剂用量低,反应原子经济性高;4)选择性好。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:肉桂醇
3-Phenylprop-2-en-1-ol
Figure BDA0001542547770000023
将肉桂醛(132mg,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:92%
1H NMR(500MHz,CDCl3)δ7.36(d,J=7.8Hz,2H),7.29(t,J=7.6Hz,2H),7.22(t,J=7.3Hz,1H),6.59(d,J=16.0Hz,1H),6.33(dt,J=15.9and 5.7Hz,1H),4.28(d,J=5.7Hz,2H),2.34(br s,1H);13C NMR(125MHz,CDCl3)δ136.6,130.9,128.5,128.4,127.6,126.4,63.5.。
实施例2:3-甲基肉桂醇
3-M-tolylprop-2-en-1-ol
Figure BDA0001542547770000031
将3-甲基肉桂醛(146mg,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,100℃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)δ7.23-7.19(m,3H),7.07(d,J=6.6Hz,1H),6.60(d,J=15.9Hz,1H),6.36(dt,J=15.9and 5.8Hz,1H),4.33(d,J=5.6Hz,2H),2.35(s,3H);13C NMR(125MHz,CDCl3)δ138.1,136.6,131.2,128.4,128.3,127.2,123.6,63.6,21.3.。
实施例3:2-甲氧基肉桂醇
3-(2-Methoxyphenyl)prop-2-en-1-ol
Figure BDA0001542547770000032
将2-甲氧基肉桂醛(162mg,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:94%
1H NMR(500MHz,CDCl3)δ7.43(d,J=7.6Hz,1H),7.24-7.21(m,1H),6.92(t,J=7.5Hz,2H),6.87(d,J=8.2Hz,1H),6.38(dt,J=16.1and 5.9Hz,1H),4.32(d,J=5.9Hz,2H),3.84(s,3H),1.83(br s,1H);13C NMR(125MHz,CDCl3)δ156.7,129.2,128.7,126.9,126.1,125.7,120.6,110.8,64.1,55.4.。
实施例4:4-溴肉桂醇
3-(4-Bromophenyl)prop-2-en-1-ol
Figure BDA0001542547770000033
将4-溴肉桂醛(211mg,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,100℃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:97%
1H NMR(500MHz,CDCl3)δ7.45(d,J=8.5Hz,2H),7.25(d,J=8.5Hz,2H),6.57(d,J=16.0Hz,1H),6.36(dt,J=15.9and 5.6Hz,1H),4.32(dd,J J=1.45and 5.6Hz,2H),1.63(br s,1H);13C NMR(125MHz,CDCl3)δ135.6,131.7,129.8,129.7,129.3,128.0,121.4,63.5,63.4.。
实施例5:2-硝基肉桂醇
3-(2-Nitrophenyl)prop-2-en-1-ol
Figure BDA0001542547770000041
将2-硝基肉桂醛(177mg,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:95%
1H NMR(500MHz,CDCl3)δ7.93(d,J=8.2Hz,1H),7.61-7.55(m,2H),7.40(t,J=7.6Hz,1H),7.10(d,J=15.7Hz,1H),6.35(dt,J=15.8and 5.3Hz,1H),4.39(d,J=4.9Hz,2H),1.99(br s,1H);13C NMR(125MHz,CDCl3)δ147.8,134.1,133.1,132.5,128.7,128.1,125.8,124.5,63.2.。
实施例6:α-甲基肉桂醇
2-Methyl-3-phenylprop-2-en-1-ol
Figure BDA0001542547770000042
将α-甲基肉桂醛(146mg,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)δ7.33(t,J=7.6Hz,2H),7.28(d,J=7.5Hz,2H),7.24-7.20(m,1H),6.52(s,1H),4.17(s,2H),2.15(br s,1H),1.89(s,3H);13C NMR(125MHz,CDCl3)δ137.6,137.5,128.8,128.1,126.4,125.0,68.9,15.2.。
实施例7:α-戊基肉桂醇
2-Benzylideneheptan-1-ol
Figure BDA0001542547770000043
将α-戊基肉桂醛(202mg,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)δ7.39(t,J=7.6Hz,2H),7.31-7.26(m,3H),6.59(s,1H),4.28(s,2H),2.34(t,J=8.1Hz,2H),1.86(br s,1H),1.59-1.53(m,2H),1.36-1.35(m,4H),0.95-0.92(t,J=6.6Hz,3H).13C NMR(125MHz,CDCl3)δ142.4,137.5,128.6,128.1,126.4,125.2,66.9,32.0,28.7,28.0,22.4,14.0.。
实施例8:α-己基肉桂醇
2-Benzylideneoctan-1-ol
Figure BDA0001542547770000051
将α-己基肉桂醛(216mg,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(t,J=7.6Hz,2H),7.25-7.20(m,3H),6.52(s,1H),4.22(s,2H),2.29(t,J=8.1Hz,2H),1.56(br s,1H),1.52-1.46(m,2H),1.32-1.26(m,6H),0.87(t,J=6.9Hz,3H).13C NMR(125MHz,CDCl3)δ142.4,137.5,128.6,128.1,126.4,125.3,67.0,31.6,29.5,28.7,28.3,22.6,14.0.。
实施例9:9-蒽丙烯醇
3-(Anthracen-9-yl)prop-2-en-1-ol
Figure BDA0001542547770000052
将9-蒽丙烯醛(232mg,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:98%
1H NMR(500MHz,CDCl3)δ8.35(s,1H),8.27-8.25(m,2H),7.97-7.95(m,2H),7.44-7.42(m,4H),7.37(d,J=16.2Hz,1H),6.22-6.16(m,1H),4.57(d,J=5.1Hz,2H),1.93(brs,1H);13C NMR(125MHz,CDCl3)δ137.2,132.1,131.3,129.4,128.6,126.6,126.3,125.8,125.4,125.1,63.8.ESI-HRMS m/z calcd for C17H15O[M+H]+235.1117,found 235.1116.。
实施例10:2-呋喃丙烯醇
3-(Furan-2-yl)prop-2-en-1-ol
Figure BDA0001542547770000061
将2-呋喃丙烯醛(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,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:92%
1H NMR(500MHz,CDCl3)δ7.34(s,1H),6.45(d,J=15.9Hz,1H),6.37-6.36(m,1H),6.29(dt,J=15.8and 5.6Hz,1H),6.24-6.23(d,J=3.2Hz,1H),4.29(d,J=5.5Hz,2H),1.85(br s,1H);13C NMR(125MHz,CDCl3)δ152.3,142.0,127.2,119.2,111.2,107.9,63.2.。
实施例11:2-甲基-2-戊烯醇
2-Methylpent-2-en-1-ol
Figure BDA0001542547770000062
将2-甲基-2-戊烯醛(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:80%
1H NMR(500MHz,CDCl3)δ5.42(td,J=7.1and 1.2Hz,1H),4.01(s,2H),2.09-2.03(m,2H),1.67(s,3H),1.22(d,J=6.2Hz,1H),0.98(t,J=7.6Hz,3H);13C NMR(125MHz,CDCl3)δ134.0,128.1,68.8,20.8,14.0,13.4.。
实施例12:2-乙基-2-己烯醇
2-Ethylhex-2-en-1-ol
Figure BDA0001542547770000063
将2-乙基-2-己烯醛(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)δ5.39(t,J=7.3Hz,1H),4.06(s,2H),2.13(q,J=7.6Hz,2H),2.04(q,J=7.4Hz,2H),1.42-1.37(m,2H),1.01(t,J=7.6Hz,3H),0.92(t,J=7.4Hz,3H);13C NMR(125MHz,CDCl3)δ1407,126.4,66.9,29.4,22.9,21.0,13.9,13.2.。
实施例13:3-环己烯甲醇
Cyclohex-3-enylmethanol
Figure BDA0001542547770000064
将3-环己烯甲醛(110mg,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)δ5.70-5.65(m,2H),3.55-3.52(m,2H),2.13-2.07(m,4H),1.82-1.71(m,3H),1.29-1.26(m,1H);13C NMR(125MHz,CDCl3)δ127.1,125.8,67.7,36.2,28.0,25.1,24.6.。
实施例14:5-降冰片烯-2-甲醇
5-Norbornene-2-methanol
Figure BDA0001542547770000071
将5-降冰片烯-2-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,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)δ6.15-6.13(m,endo,0.8H),6.12-6.10(m,exo,0.2H),6.08-6.06(m,exo,0.2H),5.97-5.95(m,endo,0.8H),3.72(dd,J=6.5and 10.6Hz,exo,0.2H),3.55-3.52(m,exo,0.2H),3.41(dd,J=6.6and 10.4Hz,endo,0.8H),3.27-3.23(m,endo,0.8H),2.93(s,endo,0.8H),2.81(s,endo,0.8H),2.75(s,exo,0.2H),2.31-2.27(m,endo,0.8H),1.84-1.79(m,endo,0.8H),1.64-1.63(m,exo,0.2H),1.62-1.59(m,exo,0.2H),1.46(d,J=7.8Hz,endo,0.8H),1.35-1.33(m,exo,0.2H),1.30-1.27(m,exo,0.2H),1.23-1.20(m,exo,0.2H),1.11(dt,J=3.9and 11.6Hz,exo,0.2H),0.52(m,endo,0.8H);13CNMR(125MHz,CDCl3)δ137.3(endo),136.7(exo),136.4(exo),132.1(endo),67.4(exo),66.4(endo),49.4(endo),44.9(exo),43.5(endo),43.2(exo),42.1(endo),41.8(exo),41.6(endo),41.4(exo),29.5(exo),28.7(endo).。
实施例15:柠檬醇
3,7-Dimethyl-2,6-octadienol
Figure BDA0001542547770000072
将柠檬醛(152mg,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)δ5.44-5.39(m,1H),5.11-5.08(m,1H),4.14-4.07(m,2H),2.11-2.02(m,4H),1.75-1.60(m,10H);13C NMR(125MHz,CDCl3)δ139.5(trans),139.2(cis),132.2(cis),131.5(trans),124.4(cis),123.8(trans),123.7(cis),123.3(trans),59.1(trans),58.7(cis),39.4(trans),31.9(cis),26.4(cis),26.3(trans),25.5(cis+trans),23.3(cis),17.5(trans),17.5(cis),16.1(trans).。

Claims (5)

1.合成不饱和伯醇的方法,其特征是,包括
Figure FDA0003039721280000011
由不饱和醛Ⅱ
Figure FDA0003039721280000012
在过渡金属铱催化剂存在下,经加氢生成目标产物Ⅰ,
其中,
R1选自烷基、芳基、甲基苯基、甲氧基苯基、硝基苯基、卤代苯基;
R2选自甲基、乙基、戊基、己基;
过渡金属铱催化剂的结构如下:
Figure FDA0003039721280000013
2.根据权利要求1所述的合成 不饱和伯醇的方法,其特征是,催化剂用量为不饱和醛Ⅱ的0.2mol%。
3.根据权利要求1所述的合成 不饱和伯醇的方法,其特征是,反应在82-120℃进行。
4.根据权利要求1所述的合成 不饱和伯醇的方法,其特征是,反应时间为6-12小时。
5.根据权利要求1所述的合成 不饱和伯醇的方法,其特征是,反应在异丙醇存在下进行。
CN201810017911.3A 2018-01-09 2018-01-09 一种合成不饱和伯醇的方法 Expired - Fee Related CN110015947B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810017911.3A CN110015947B (zh) 2018-01-09 2018-01-09 一种合成不饱和伯醇的方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810017911.3A CN110015947B (zh) 2018-01-09 2018-01-09 一种合成不饱和伯醇的方法

Publications (2)

Publication Number Publication Date
CN110015947A CN110015947A (zh) 2019-07-16
CN110015947B true CN110015947B (zh) 2021-08-03

Family

ID=67187647

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810017911.3A Expired - Fee Related CN110015947B (zh) 2018-01-09 2018-01-09 一种合成不饱和伯醇的方法

Country Status (1)

Country Link
CN (1) CN110015947B (zh)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111732977A (zh) * 2020-05-22 2020-10-02 浙江大学 一种呋喃基丙烯醛原位加氢制备呋喃醇生物柴油的方法
CN111925275B (zh) * 2020-08-31 2021-11-02 江南大学 一种柠檬醛催化加氢制备香叶醇的方法
CN113024418B (zh) * 2021-03-24 2023-01-24 河北工业大学 一种异丙醇作氢源合成脂环族氨基甲酸酯的方法
CN113105304B (zh) * 2021-04-08 2022-03-29 上海橡实化学有限公司 一种在水相中合成不饱和伯醇的方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5347056A (en) * 1992-08-07 1994-09-13 Mitsubishi Petrochemical Company, Ltd. Process for producing unsaturated alcohols
CN104945208A (zh) * 2015-05-14 2015-09-30 大连理工大学 一种由α,β-不饱和醛酮制备烯丙醇类化合物的方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5347056A (en) * 1992-08-07 1994-09-13 Mitsubishi Petrochemical Company, Ltd. Process for producing unsaturated alcohols
CN104945208A (zh) * 2015-05-14 2015-09-30 大连理工大学 一种由α,β-不饱和醛酮制备烯丙醇类化合物的方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
On Water and in Air: Fast and Highly Chemoselective Transfer Hydrogenation of Aldehydes with Iridium Catalysts;Xiaofeng Wu 等;《Angew.Chem.Int.Ed.》;20060908;第45卷;第6721页Table 3和第6722页Experimental Section *
Synthesis and Reactivity of Heteroditopic Dicarbene Rhodium(I) and Iridium(I) Complexes Bearing Chelating 1,2,3-Triazolylidene−Imidazolylidene Ligands;Soraya N. Sluijter 等;《Organometallics》;20141027;第33卷;第6393页Table 2 *
Thermoregulated phase-transfer iridium nanoparticle catalyst: highly selective hydrogenation of the C=O bond for α,β-unsaturated aldehydes and the C=C bond for α,β-unsaturated ketones;Wenjiang Li 等;《Catal.Sci.Technol.》;20160906;第6卷;第7388页Table 3 *

Also Published As

Publication number Publication date
CN110015947A (zh) 2019-07-16

Similar Documents

Publication Publication Date Title
CN110015947B (zh) 一种合成不饱和伯醇的方法
AU2017224165B2 (en) Process for preparing terpinene-4-ol
CN106748696B (zh) 一种甲基紫罗兰酮及其中间体的制备方法
Siddiqui Bis [(L) prolinato-N, O] Zn–water: A green catalytic system for the synthesis of 3, 4-dihydropyrimidin-2 (1H)-ones via the Biginelli reaction
Włodarczyk et al. Intramolecular cationic cyclization of β-hydroxyalkylphosphine oxides—a route towards the benzophosphorinane core
JP2006160663A (ja) 1,1’−ビス(2−ヒドロキシナフチル)類の製造方法
CN109384644B (zh) 一种合成伯醇的方法
JP6558742B2 (ja) アルデヒド化合物の製造方法およびアセタール化合物
Albrow et al. Synthesis of an octahydro-1, 1′-binaphthyl thioether ligand and comparison with unhydrogenated binaphthyl analogues
CN109422654B (zh) 合成脂肪胺甲基化化合物的方法
CN107827723B (zh) 一种长链二酮合成方法
Shiga et al. Condensation Reaction of Ferrocene with Carbonyl Compounds
EP3468943B1 (en) Process for the preparation of alcohols from alfa,beta-unsaturated aldehydes and ketones
US4262153A (en) Decomposition of hydroperoxides using metal complex catalysts
Suzuki et al. A novel route to α, β-unsaturated esters via a Reformatsky-type reaction using sodium telluride
US4279829A (en) Metal complex catalysts
CN109836373B (zh) 一种维生素b6的环保制备及尾气循环利用的方法
JP5854345B2 (ja) 二量体の製造方法
JP2017071556A (ja) オキソバナジウム錯体を用いたカルボン酸プレニル類及びプレノール類の製造方法
CN111018664B (zh) 一种2-烷基-1,3-丙二醇类化合物的合成方法
JP2016124788A (ja) 長鎖ケトアルコールの製造方法およびそれを還元してなる長鎖ジオール
CA1281731C (en) Process for production of oxime derivatives
Qin et al. Reaction of Aldehydes and 5, 5-Dimethyl-1, 3-cyclohexanedione in the Presence of Surfactants in Water
JPH04253935A (ja) 2−(4−クロルフエニル)−3−メチル酪酸の製法
CN107973703B (zh) 一种芳基烯烃的合成方法

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20210803

CF01 Termination of patent right due to non-payment of annual fee