CN114605462A - 一种钴催化制备烯丙基硅衍生物的方法 - Google Patents
一种钴催化制备烯丙基硅衍生物的方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 19
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 10
- 239000010941 cobalt Substances 0.000 title claims abstract description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910000077 silane Inorganic materials 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
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- 239000002994 raw material Substances 0.000 claims abstract 2
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- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000003446 ligand Substances 0.000 claims description 10
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- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims description 5
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- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 claims description 3
- WGOBPPNNYVSJTE-UHFFFAOYSA-N 1-diphenylphosphanylpropan-2-yl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)C(C)CP(C=1C=CC=CC=1)C1=CC=CC=C1 WGOBPPNNYVSJTE-UHFFFAOYSA-N 0.000 claims description 3
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims description 3
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 8
- 125000001424 substituent group Chemical group 0.000 claims 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 3
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 2
- 125000003118 aryl group Chemical group 0.000 claims 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 2
- 229910052794 bromium Inorganic materials 0.000 claims 2
- 239000000460 chlorine Substances 0.000 claims 2
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims 2
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- XMSZANIMCDLNKA-UHFFFAOYSA-N methyl hypofluorite Chemical compound COF XMSZANIMCDLNKA-UHFFFAOYSA-N 0.000 claims 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims 2
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
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- 238000005580 one pot reaction Methods 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 14
- 238000001228 spectrum Methods 0.000 description 11
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
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- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000012230 colorless oil Substances 0.000 description 7
- 235000019439 ethyl acetate Nutrition 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 6
- 230000005311 nuclear magnetism Effects 0.000 description 5
- 238000001819 mass spectrum Methods 0.000 description 4
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- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- 238000004611 spectroscopical analysis Methods 0.000 description 2
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- 239000002028 Biomass Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0896—Compounds with a Si-H linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/0827—Syntheses with formation of a Si-C bond
- C07F7/0829—Hydrosilylation reactions
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Abstract
本发明涉及一种制备钴催化萜烯类硅化合物的方法。具体地说在钴催化的条件下萜烯、硅烷经过一锅法制备。本发明由简单易得的原料和催化剂出发、经硅氢化反应得到一系列萜烯类硅化合物化合物。
Description
技术领域
本发明涉及一种钴催化制备萜烯类硅化合物的方法。
背景技术
由于有机硅化合物独特的结构,兼备了无机材料与有机材料的性能,具有表面张力低、粘温系数小、压缩性高、气体渗透性高等基本性质,并具有耐高低温、电气绝缘、耐氧化稳定性、耐候性、难燃、憎水、耐腐蚀、无毒无味以及生理惰性等优异特性,广泛应用于航空航天、电子电气、建筑、运输、化工、纺织、食品、轻工、医疗等行业,其中有机硅主要应用于密封、粘合、润滑、涂层、表面活性、脱模、消泡、抑泡、防水、防潮、惰性填充等。随着有机硅数量和品种的持续增长,应用领域不断拓宽,形成化工新材料界独树一帜的重要产品体系,许多品种是其他化学品无法替代而又必不可少的,具有巨大的开发潜力。
与以往萜烯硅的合成方法相比,本发明通过高区域选择性生物质萜类硅氢化反应直构筑了烯丙基硅类化合物。
总之,本文描述了一种钴催化高区域选择性的制备萜类硅衍生物的方法。
发明内容
本发明的目的在于提供一种钴催化高区域选择性的制备萜类硅衍生物的方法。
反应方程式1:萜烯硅衍生物的合成
具体操作步骤如下(反应方程式1):
于反应器中进行反应,首先加入催化剂和配体及溶剂,搅拌1分钟,然后加还原剂、硅烷1、烯烃2、于20-100℃下反应,反应时间2.0-24.0小时;反应结束后,分离得到烯丙基硅衍生物3。
硅烷1与烯烃2的摩尔用量比为1:1-3,优选比为1:1.5。
催化剂为醋酸钴、溴化钴、乙酰丙酮钴、氯化钴中的一种或两种以上,优选乙酰丙酮钴;催化剂的用量为硅烷1用量的1mol%-10mol%,优选5mol%。
配体为1,2-双(二苯基膦)甲烷、1,2-双(二苯基膦)乙烷、1,2-双(二苯基膦)丙烷、4,5-双(二苯基膦)-9,9-二甲基氧杂蒽中的一种或两种以上;优选4,5-双(二苯基膦)-9,9-二甲基氧杂蒽。配体用量为硅烷1用量的1mol%-10mol%,优选5mol%。
还原剂为三乙基硼氢化钠、二乙基锌、乙基溴化镁中的一种或两种以上,优选三乙基硼氢化钠;还原剂的用量为硅烷1用量的1mol%-50mol%,优选10mol%。
溶剂为正己烷、甲苯、乙醚、甲基叔丁基醚、四氢呋喃中的一种或两种以上,优选正己烷;溶剂的用量为每毫摩尔硅烷1用溶剂0.1-5.0毫升,优选1.0毫升。
本发明有以下优点:
首先,反应具有高度的区域选择性,与萜烯类底物反应得到专一性的4,1-加成烯丙基硅化合物。有利于其进一步转化衍生材料制品。其次,反应需要用到的原料萜烯类底物简单易得,并且属于大宗化学品,价格便宜。最后,本反应体系中用到的催化剂为简单的钴催化剂,于已报道的钴类催化剂相比,此反应体系区域选择性高,产物转一。
具体实施方式
为了更好地理解本发明,通过以下实例进行说明。实施例1-7的反应原料及结果见表1。
表1不同取代硅烷、萜烯的反应结果
实施例1
于反应器中进行反应,首先加入催化剂乙酰丙酮钴0.02mmoL(用量为硅烷1量的10mol%)和配体4,5-双(二苯基膦)-9,9-二甲基氧杂蒽0.02mmoL(用量为硅烷1量的10mol%)及溶剂正己烷(1.0mL),搅拌1分钟,然后加还原剂三乙基硼氢化钠0.04mmoL(用量为硅烷1量的20mol%)、硅烷1a(0.2mmol)、烯烃2a(0.3mmol)、于40℃下反应,反应时间2.0小时;反应结束后,经过柱层析分离得到烯丙基硅化合物3a收率为81%,化合物经过红外、核磁(氢谱和碳谱)、高分辨质谱鉴定结构。
检测数据如下:
3a:Colorless oil,41.0mg,81%yield,Rf=0.8(PE/EtOAc 100/1).1H NMR(400MHz,CDCl3)δ7.61–7.54(m,4H),7.41–7.30(m,6H),5.13(q,J=6.6Hz,1H),4.90(t,J=4.0Hz,1H),2.09(d,J=4.0Hz,2H),1.62(t,J=1.5Hz,3H),1.37(d,J=6.7Hz,3H).13C NMR(100MHz,CDCl3)δ135.21,134.45,132.19,129.66,127.94,117.79,25.76,18.71,13.71.HRMS calculated for C17H21Si[M+H]+253.1413,found 253.1413.
实施例2:
操作过程和条件同实施例1,与实施例1不同之处在于,除表1中表述的区别之外,催化剂为醋酸钴,添加量为20%(用量为硅烷1量的20mol%);还原剂为二乙基锌,添加量为40%产物(用量为硅烷1量的40mol%)。3b收率为67%,化合物经过核磁(氢谱和碳谱)、高分辨质谱鉴定结构。
3b:Colorless oil,35.4mg,67%yield,Rf=0.8(petroleum ether/EtOAc 100/1).1H NMR(400MHz,Chloroform-d)δ7.60–7.53(m,2H),7.51–7.44(m,2H),7.41–7.31(m,3H),7.18(d,J=7.5Hz,2H),5.12(q,J=6.7Hz,1H),4.88(td,J=3.9,1.2Hz,1H),2.35(s,3H),2.08(d,J=4.0Hz,2H),1.62(q,J=1.5Hz,3H),1.38(d,J=6.7Hz,2H).13C NMR(100MHz,Chloroform-d)δ139.59,135.24,135.17,134.76,132.35,130.67,129.55,128.79,127.88,117.64,25.75,21.57,18.80,13.71.
实施例3:
操作过程和条件同实施例1,与实施例1不同之处在于,除表1中表述的区别之外,溶剂为甲苯,产物3c收率为63%,化合物经过核磁(氢谱和碳谱)、高分辨质谱鉴定结构。
3c:Colorless oil,38.7mg,63%yield,Rf=0.8(petroleum ether/EtOAc 100/1).1H NMR(400MHz,Chloroform-d)δ7.58(dt,J=6.5,1.7Hz,2H),7.54–7.49(m,2H),7.40–7.33(m,5H),5.12(q,J=6.8Hz,1H),4.89(t,J=3.9Hz,1H),2.08(d,J=4.1Hz,2H),1.62(t,J=1.5Hz,3H),1.37(dd,J=6.7,1.6Hz,3H),1.31(s,9H).13C NMR(100MHz,Chloroform-d)δ152.68,135.22,135.04,134.71,132.37,130.79,129.55,127.86,124.92,117.63,34.73,31.25,25.76,18.80,13.69.
实施例4:
操作过程和条件同实施例1,与实施例1不同之处在于,除表1中表述的区别之外,反应温度为80℃,产物3d收率为71%,化合物经过核磁(氢谱和碳谱)。
3d:Colorless oil,39.8mg,71%yield,Rf=0.8(petroleum ether/EtOAc 100/1).1H NMR(400MHz,Chloroform-d)δ7.58–7.54(m,2H),7.50(d,J=8.1Hz,2H),7.36(dd,J=10.2,7.0Hz,3H),6.91(d,J=8.1Hz,2H),5.12(q,J=6.9Hz,1H),4.88(t,J=4.0Hz,1H),3.80(s,3H),2.06(d,J=4.0Hz,2H),1.65–1.59(m,3H),1.37(d,J=6.7Hz,3H).13C NMR(100MHz,Chloroform-d)δ160.93,136.69,135.13,134.91,132.36,129.54,127.88,125.04,117.61,113.74,55.03,25.75,18.93,13.70.
实施例5:
操作过程和条件同实施例1,与实施例1不同之处在于,除表1中表述的区别之外,还原剂为乙基溴化镁,添加量为20%(用量为硅烷1量的20mol%),产物3e收率为69%,化合物经过核磁(氢谱和碳谱)。
3e:Colorless oil,45.3mg,69%yield,Rf=0.8(petroleum ether/EtOAc 100/1).1H NMR(400MHz,Chloroform-d)δ7.66–7.58(m,8H),7.45–7.33(m,6H),5.14(q,J=6.8Hz,1H),4.95(t,J=4.0Hz,1H),2.12(d,J=4.0Hz,2H),1.65(s,3H),1.39(d,J=6.8Hz,3H).13C NMR(100MHz,Chloroform-d)δ142.38,140.95,135.72,135.25,134.43,133.18,132.20,129.73,128.85,128.00,127.55,127.19,126.66,117.87,25.82,18.77,13.79.
实施例6:
操作过程和条件同实施例1,与实施例1不同之处在于,除表1中表述的区别之外,醋酸钴催化剂用量为5%(用量为硅烷1量的5mol%),配体为1,2-双(二苯基膦)乙烷,用量为10%(用量为硅烷1量的10mol%)。产物3f收率为62%,化合物经过核磁(氢谱和碳谱)、高分辨质谱鉴定结构。
3f:Colorless oil,39.6mg,62%yield,Rf=0.8(petroleum Zether/EtOAc 100/1).1H NMR(400MHz,Chloroform-d)1H NMR(400MHz,Chloroform-d)δ7.65–7.49(m,4H),7.43–7.27(m,6H),5.14(q,J=6.7Hz,1H),5.01(t,J=6.8Hz,1H),4.90(t,J=4.0Hz,1H),2.10(d,J=4.0Hz,2H),2.04(q,J=7.4Hz,2H),1.90(t,J=7.8Hz,2H),1.65(s,3H),1.55(s,3H),1.38(d,J=6.7Hz,3H).13C NMR(100MHz,Chloroform-d)δ135.99,135.20,134.48,131.35,129.62,127.91,124.34,117.22,38.72,26.77,25.71,17.70,16.97,13.69.HRMScalculated for C22H29Si[M+H]+321.2039,found 321.2036
实施例7:
操作过程和条件同实施例1,与实施例1不同之处在于,除表1中表述的区别之外,配体为1,2-双(二苯基膦)丙烷,用量为5%(用量为硅烷1量的5mol%),产物3g收率为66%,化合物经过红外、核磁(氢谱和碳谱)、高分辨质谱鉴定结构。
3g:Colorless oil,59.8mg,66%yield,Rf=0.8(petroleum Zether/EtOAc 100/1).1H NMR(400MHz,Chloroform-d)δ7.52(d,J=7.0Hz,4H),7.41–7.24(m,6H),5.09(q,J=6.8Hz,1H),4.85(d,J=4.1Hz,1H),2.04(d,J=3.9Hz,2H),1.80(t,J=7.6Hz,2H),1.43–1.30(m,5H),1.27–1.19(m,2H),1.10(s,6H),0.80(s,9H),-0.00(s,6H).13C NMR(100MHz,Chloroform-d)δ136.20,135.16,134.50,129.56,127.86,117.06,73.44,44.68,39.13,29.81,25.88,22.66,18.10,16.70,13.62,-2.03.HRMS calculated for C28H45OSi[M+H]+453.3009,found 453.3005
应用实施例1:
反应方程式2:有机硅聚合物合成
产物3a可以通过进一步聚合反应,简单的转化为润滑有机硅聚合材料。具体操作如下(式2):
在氮气保护条件下,3a(0.2mmol)溶解于甲苯中(5.0mL)中,加入预制钴催化剂(3a的1mmol%),然后120℃搅拌24h,常温时加质量浓度10%盐酸10mL淬灭90。之后,用乙醚3*10mL萃取,无水硫酸钠干燥,旋蒸得到无色油状液体。化合物经过核磁(氢谱),分子量范围1000-6500。
Claims (7)
1.一种钴催化制备萜烯类硅化合物的方法,其特征在于:
以下式所示的萜烯类底物1、硅烷2为原料生成烯丙基硅衍生物3,反应式如下:
其中R为C1-C20烷基,优选为C1-C6烷基,更优选为甲基或乙基;
R1为甲基、乙基、异丙基、正己基、环己基、苯基、或苯环上带有取代基的芳基,苯环上的取代基为甲基、甲氧基、氟、氯、溴中的1-2种,苯环上取代基的个数为1-2个;
R2选甲基、乙基、异丙基、正己基、环己基、苯基、或苯环上带有取代基的芳基,苯环上的取代基为甲基、甲氧基、氟、氯、溴中的1-2种,苯环上取代基的个数为1-2个;
催化剂为含钴元素催化剂;
配体为1,2-双(二苯基膦)甲烷、1,2-双(二苯基膦)乙烷、1,2-双(二苯基膦)丙烷、4,5-双(二苯基膦)-9,9-二甲基氧杂蒽中的一种或两种以上。
2.按照权利要求1所述的制备烯丙基硅化合物的方法,其特征在于:
具体操作步骤如下:
于反应器中进行反应,首先加入催化剂和配体及溶剂,搅拌1分钟以上,然后加还原剂、硅烷1、萜烯2,于20-100℃下反应,优选40℃;反应时间0.5-24小时,优选2.0小时;反应结束后,分离得到烯丙基硅衍生物3。
3.按照权利要求2所述的方法,其特征在于:
硅烷1与萜烯2的摩尔用量比为1:1-3,优选比为1:10-1.8,更优选1:1.5。
4.按照权利要求2所述的方法,其特征在于:
催化剂为醋酸钴、溴化钴、乙酰丙酮钴、氯化钴中的一种或两种以上,优选乙酰丙酮钴;催化剂的用量为硅烷1用量的1mol%-10mol%,优选5mol%。
5.按照权利要求2所述的方法,其特征在于:
配体用量为硅烷1用量的1mol%-10mol%,优选5mol%。
6.按照权利要求2所述的方法,其特征在于:
还原剂为三乙基硼氢化钠、二乙基锌、乙基溴化镁中的一种或两种以上,优选三乙基硼氢化钠;还原剂的用量为硅烷1用量的1mol%-50mol%,优选10mol%。
7.按照权利要求2所述的方法,其特征在于:
溶剂为正己烷、甲苯、乙醚、甲基叔丁基醚、四氢呋喃中的一种或两种以上,优选正己烷;溶剂的用量为每毫摩尔硅烷1用溶剂0.1-5.0毫升,优选1.0毫升。
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