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 PDFInfo
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- GUUHFMWKWLOQMM-NTCAYCPXSA-N alpha-hexylcinnamaldehyde Chemical compound CCCCCC\C(C=O)=C/C1=CC=CC=C1 GUUHFMWKWLOQMM-NTCAYCPXSA-N 0.000 description 1
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- AJIBZRIAUXVGQJ-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-5-carbaldehyde Chemical compound C1C2C(C=O)CC1C=C2 AJIBZRIAUXVGQJ-UHFFFAOYSA-N 0.000 description 1
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- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
- C07C29/136—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
- C07C29/14—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 a —CHO group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
- C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic 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
- C07D307/38—Heterocyclic 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
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
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- 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
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)
由不饱和醛(式Ⅱ)
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
由不饱和醛Ⅱ
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：
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。
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