CN108586512A - 一种新型乙烯基硅基化合物的制备方法 - Google Patents
一种新型乙烯基硅基化合物的制备方法 Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 24
- 239000010703 silicon Substances 0.000 title claims abstract description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 23
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 239000005977 Ethylene Substances 0.000 title claims abstract description 14
- 239000010948 rhodium Substances 0.000 claims abstract description 14
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 12
- ARLJCLKHRZGWGL-UHFFFAOYSA-N ethenylsilicon Chemical compound [Si]C=C ARLJCLKHRZGWGL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- -1 alkyl compound Chemical class 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- ADGFUTSPEKVFKD-UHFFFAOYSA-N carbonyl dichloride;rhodium Chemical class [Rh].ClC(Cl)=O ADGFUTSPEKVFKD-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 42
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims 2
- 239000004575 stone Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000012450 pharmaceutical intermediate Substances 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 description 10
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 238000004440 column chromatography Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- WYNCHZVNFNFDNH-UHFFFAOYSA-N Oxazolidine Chemical compound C1COCN1 WYNCHZVNFNFDNH-UHFFFAOYSA-N 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- ICGWCNWBIXCLOU-UHFFFAOYSA-N 2-ethynyl-1,3-dihydropyrazole Chemical compound C(#C)N1NC=CC1 ICGWCNWBIXCLOU-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BZLZKLMROPIZSR-UHFFFAOYSA-N triphenylsilicon Chemical compound C1=CC=CC=C1[Si](C=1C=CC=CC=1)C1=CC=CC=C1 BZLZKLMROPIZSR-UHFFFAOYSA-N 0.000 description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- 238000006732 Fleming-Tamao oxidation reaction Methods 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 229910004161 SiNa Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 238000007336 electrophilic substitution reaction Methods 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- OKHRRIGNGQFVEE-UHFFFAOYSA-N methyl(diphenyl)silicon Chemical compound C=1C=CC=CC=1[Si](C)C1=CC=CC=C1 OKHRRIGNGQFVEE-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000002904 solvent Substances 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
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
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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
- C07F7/0803—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
本发明属于有机合成技术领域,提供了一种新型乙烯基硅基化合物的制备方法,在有机溶剂中,在四羰基二氯化铑二聚体[Rh(CO)2Cl]2催化剂作用下,催化炔胺类化合物与有机硅烷类化合物制备(Z)‑β‑型乙烯基硅基化合物。本发明中(Z)‑β‑型乙烯基硅基化合物的制备方法反应条件温和,产物收率不低于65%。该制备方法的反应条件温和、绿色、反应效率高,更适合规模化生产要求,制备得到的(Z)‑β‑型乙烯基硅基化合物可以转化为很多药物中间体。
Description
技术领域
本发明属于有机合成技术领域,涉及一种新型乙烯基硅基化合物的制备方法。
背景技术
乙烯基硅基化合物是一类重要的有机合成中间体,可以通过交叉偶联反应,Tamao-Fleming氧化反应,亲电取代反应以及基团转移聚合等方法合成结构多样的有机药物中间体。近年来,已有一系列文献或专利报道了乙烯基硅基化合物的制备方法。
使用硅烷对炔烃进行硅氢化反应是最直接和最高原子经济性的方法(J.Am.Chem.Soc.2015,137,6857.及Angew.Chem.Int.Ed.,2012,51,3225),该反应受到广泛研究与关注。但是,对于内炔的硅氢化反应,很多情况下生成Z/E和α/β四种混合的乙烯基硅基化合物(J.Am.Chem.Soc.2010,132,11926.及J.Am.Chem.Soc.2005,127,17644.)。如何改变内炔硅氢化反应的区域选择性和立体选择性是我们关注的重点。虽然目前已有一些改变内炔硅氢化反应的区域选择性和立体选择性的方法被报道出来,但是对于(Z)-β-型乙烯基硅基化合物的制备技术目前尚未见公开报道。因此研究其制备方法有重要的意义。
本发明采用了各种炔胺和有机硅烷为原料,使用2.5mol%[Rh(CO)2Cl]2作为催化剂,在室温的条件下,以65%~81%的收率得到(Z)-β-型乙烯基硅基化合物。
发明内容
本发明要解决的技术问题是提供一种合成乙烯基硅基化合物的方法。
本发明的技术方案:
一种新型乙烯基硅基化合物的制备方法,步骤如下:
在有机溶剂中,在四羰基二氯化铑二聚体[Rh(CO)2Cl]2催化剂作用下,催化炔胺类化合物与有机硅烷类化合物制备(Z)-β-型乙烯基硅基化合物,反应式如下:
其中,R1和R2为氢原子、烷基、烷氧基或芳基,R1和R2相同或不同;
R3为烷基、烷氧基或芳基;
R4,R5和R6为烷基或芳基,R4,R5和R6相同或不同;
I为炔胺类化合物;
II为有机硅烷类化合物;
反应温度为25℃~65℃,反应时间为8h~24h,制备得到收率不低于65%的(Z)-β-型乙烯基硅基化合物。
所述的炔胺类化合物与有机硅烷类化合物的摩尔比为1:2,炔胺类化合物的浓度为0.01-0.1mmol/ml。
所述的[Rh(CO)2Cl]2的用量为炔胺类化合物的0.5~50mol%。
所述的有机溶剂为乙腈、苯、甲苯、乙醚、甲基叔丁基醚、二氯甲烷、四氢呋喃、三氟甲苯、环己烷、石油醚中的一种或两种以上混合,优选溶剂为乙腈、甲苯或氯仿。
本发明的有益效果:本发明中(Z)-β-型乙烯基硅基化合物的制备方法反应条件温和,产物收率不低于65%。该制备方法的反应条件温和、绿色、反应效率高,更适合规模化生产要求,制备得到的(Z)-β-型乙烯基硅基化合物可以转化为很多药物中间体。
具体实施方式
以下结合技术方案,进一步说明本发明的具体实施方式。
实施例1:(Z)-3(2-苯基-2-(三乙基硅基)乙烯基)恶唑烷-2-酮的制备
在氮气下,将3-苯基乙炔基-吡唑啉2-酮(0.2mmol,37.4mg)溶于乙腈(2mL)中,再加入三乙基硅烷(0.4mmol,46.4mg)及[Rh(CO)2Cl]2(0.005mmol,1.9mg),室温下搅拌反应混合物,反应12h,反应完后柱层析分离得到黄色油状产物46.1mg,Z/E=15:1,产率76%。
1H NMR(400MHz,CDCl3,TMS):δ7.29-7.25(m,2H),7.22-7.20(m,1H),7.11-7.08(m,2H),6.65(s,1H),4.42(t,J=8.0Hz,2H),3.85(t,J=8.0Hz,2H),0.92(t,J=8.0Hz,9H),0.65(q,J=8.0Hz,6H).13C NMR(125MHz,CDCl3):δ157.4,143.7,136.7,136.0,128.0,128.0,126.0,62.1,47.4,7.6,4.4.IR(KBr)ν2955,2359,1761,1598,1398,1265,1080,741,703cm-1.HRMS(EI-TOF)m/z:[M]+Calcd for C17H25NO2Si 303.1655;Found 303.1664.
实施例2:(Z)-3(2-(4-甲氧基苯基)-2-(三乙基甲硅烷基)乙烯基)恶唑烷-2-酮的制备
在氮气下,将3-对甲氧基苯基乙炔基-吡唑啉2-酮(0.2mmol,43.4mg)溶于乙腈(2mL)中,再加入三乙基硅烷(0.4mmol,46.4mg)及[Rh(CO)2Cl]2(0.005mmol,1.9mg),室温下搅拌反应混合物,反应12h,反应完后柱层析分离得到黄色油状产物46.6mg,Z/E>20:1,产率70%。
1H NMR(500MHz,CDCl3,TMS):δ7.02(d,J=10.0Hz,2H),6.81(d,J=10.0Hz,2H),6.60(s,1H),4.41(t,J=10.0Hz,2H),3.82(t,J=10.0Hz,2H),3.80(s,3H),0.92(t,J=10.0Hz,9H),0.65(q,J=10.0Hz,6H).13C NMR(125MHz,CDCl3):δ158.0,157.5,136.6,135.9,129.8,129.0,113.4,62.1,56.2,47.5,7.6,4.3.IR(KBr)ν2956,2359,1762,1590,1265,1110,742,701cm-1.HRMS(EI-TOF)m/z:[M]+Calcd for C18H27NO3Si 333.1760;Found333.1764.
实施例3:(Z)-3(2-(4-氯苯基)-2-(三乙基甲硅烷基)乙烯基)恶唑烷-2-酮的制备
在氮气下,将3-对氯苯基乙炔基-吡唑啉2-酮(0.2mmol,44.2mg)溶于乙腈(2mL)中,再加入三乙基硅烷(0.4mmol,46.4mg)及[Rh(CO)2Cl]2(0.005mmol,1.9mg),室温下搅拌反应混合物,反应12h,反应完后柱层析分离得到黄色油状产物46.5mg,Z/E=18:1,产率69%。
1H NMR(500MHz,CDCl3,TMS):δ7.24(d,J=10.0Hz,2H),7.02(d,J=10.0Hz,2H),6.65(s,1H),4.42(t,J=10.0Hz,2H),3.85(t,J=10.0Hz,2H),0.92(t,J=10.0Hz,9H),0.64(q,J=10.0Hz,6H).13C NMR(125MHz,CDCl3):δ157.3,142.3,137.1,134.2,132.0,129.4,128.1,62.1,47.2,7.6,4.4.IR(KBr)ν2957,2305,1762,1481,1264,749,705cm- 1.HRMS(EI-TOF)m/z:[M]+Calcd for C17H24ClNO2Si 337.1265;Found 337.1257.
实施例4:(Z)-1(2-苯基-2-(三乙基硅基)乙烯基)吡咯烷酮-2-酮的制备
在氮气下,将3-苯基乙炔基-吡咯烷酮2-酮(0.2mmol,45.8mg)溶于乙腈(2mL)中,再加入三乙基硅烷(0.4mmol,46.4mg)及[Rh(CO)2Cl]2(0.005mmol,1.9mg),室温下搅拌反应混合物,反应12h,反应完后柱层析分离得到黄色油状产物39.7mg,Z/E=5:1,产率66%。
1H NMR(500MHz,CDCl3,TMS):δ7.50-7.33(m,5H),7.28(s,1H),3.86(t,J=10.0Hz,2H),2.60(t,J=10.0Hz,2H),2.24(t,J=10.0Hz,2H),0.98(t,J=10.0Hz,9H),0.81(q,J=10.0Hz,6H).13C NMR(125MHz,CDCl3):δ175.1,146.4,130.3,128.2,127.1,126.5,126.1,49.4,31.3,18.5,6.8,5.3.IR(KBr)ν2876,1710,1461,1384,1265,737,703cm-1.HRMS(EI-TOF)m/z:[M]+Calcd for C18H27NOSi 301.1862;Found 301.1870.
实施例5:(Z)-(S)-4-苄基-3-(2-苯基-2-(三乙基硅基)乙烯基)恶唑烷-2-酮的制备
在氮气下,将3-苯基乙炔基-((S)-4-苄基吡唑啉)-2-酮(0.2mmol,52.6mg)溶于乙腈(2mL)中,再加入三乙基硅烷(0.4mmol,46.4mg)及[Rh(CO)2Cl]2(0.005mmol,1.9mg),室温下搅拌反应混合物,反应12h,反应完后柱层析分离得到白色固体产物58.2mg,Z/E>20:1,产率74%。
Mp=115-116℃. 1H NMR(400MHz,CDCl3,TMS):δ7.37-7.12(m,10H),6.44(s,1H),4.30-4.14(m,3H),3.23(t,J=8.0Hz,1H),2.83-2.77(m,1H),0.97(t,J=8.0Hz,9H),0.74(q,J=8.0Hz,6H).13C NMR(125MHz,CDCl3):δ156.8,143.2,143.1,135.6,135.1,129.1,129.1,128.0,127.8,127.3,126.3,66.5,60.4,38.3,7.6,3.6.IR(KBr)ν2961,2359,1759,1420,1265,1110,748,704cm-1.HRMS(EI-TOF)m/z:[M]+Calcd for C24H31NO2Si 393.2124;Found 393.2133.
实施例6:(Z)-3(2-苯基-2-(三苯基硅基)乙烯基)恶唑烷-2-酮的制备
在氮气下,将3-苯基乙炔基-吡唑啉2-酮(0.2mmol,37.4mg)溶于乙腈(2mL)中,再加入三苯基硅烷(0.4mmol,104mg)及[Rh(CO)2Cl]2(0.005mmol,1.9mg),室温下搅拌反应混合物,反应12h,反应完后柱层析分离得到黄色油状产物69.7mg,Z/E=16:1,产率78%。
1H NMR(500MHz,CDCl3,TMS):δ7.57-7.55(m,6H),7.40-7.35(m,5H),7.35-7.29(m,6H),7.00-6.98(m,4H),3.61(t,J=10.0Hz,2H),3.34(t,J=10.0Hz,2H).13C NMR(125MHz,CDCl3):δ156.9,143.2,139.4,136.1,134.3,129.7,129.2,127.9,127.6,125.8,122.9,62.2,46.9.IR(KBr)ν2920,2851,1765,1590,1390,1102,700cm-1.HRMS(EI-TOF)m/z:[M]+Calcd for C29H25NO2Si 447.1655;Found 447.1650.
实施例7:(Z)-3(2-(二甲基(苯基)甲硅烷基)-2-苯基乙烯基)恶唑烷-2-酮的制备
在氮气下,将3-苯基乙炔基-吡唑啉2-酮(0.2mmol,37.4mg)溶于乙腈(2mL)中,再加入二甲基苯基硅烷(0.4mmol,54.4mg)及[Rh(CO)2Cl]2(0.005mmol,1.9mg),室温下搅拌反应混合物,反应12h,反应完后柱层析分离得到黄色油状产物45.2mg,Z/E=15:1,产率70%。
1H NMR(400MHz,CDCl3,TMS):δ7.63-7.62(m,2H),7.39-7.18(m,8H),6.77(s,1H),3.84(t,J=8.0Hz,2H),3.38(t,J=8.0Hz,2H),0.34(s,6H).13C NMR(125MHz,CDCl3):δ157.6,144.2,139.5,137.2,134.4,130.1,129.0,128.8,127.0,125.0,113.6,62.6,47.3,0.0.IR(KBr)ν2986,2359,1758,1417,1265,1111,814,747cm-1.HRMS(ESI-TOF)m/z:[M+Na]+Calcd for C19H21NO2SiNa 346.1234,found 346.1239.
实施例8:(Z)-3(2-(甲基二苯基硅基)-2-苯基乙烯基)恶唑烷-2-酮的制备
在氮气下,将3-苯基乙炔基-吡唑啉2-酮(0.2mmol,37.4mg)溶于乙腈(2mL)中,再加入二苯基甲基硅烷(0.4mmol,79.2mg)及[Rh(CO)2Cl]2(0.005mmol,1.9mg),室温下搅拌反应混合物,反应12h,反应完后柱层析分离得到黄色油状产物55.4mg,Z/E=17:1,产率70%。
1H NMR(400 MHz,CDCl3,TMS):δ7.66-7.64(m,4H),7.40-7.38(m,6H),7.22-7.16(m,6H),3.66(t,J=8.0 Hz,2H),3.33(t,J=8.0 Hz,2H),0.39(s,3H).13C NMR(125 MHz,CDCl3):δ156.9,143.3,138.4,136.2,134.9,129.6,128.4,128.1,127.1,126.3,112.8,62.0,46.9,-0.5.IR(KBr)ν2985,1759,1398,1109,1039,747,703 cm-1.HRMS(ESI-TOF)m/z:[M+Na]+Calcd for C24H23NO2Si 408.1390;Found 408.1392.
Claims (8)
1.一种新型乙烯基硅基化合物的制备方法,其特征在于,步骤如下:
在有机溶剂中,在四羰基二氯化铑二聚体[Rh(CO)2Cl]2催化剂作用下,催化炔胺类化合物与有机硅烷类化合物制备(Z)-β-型乙烯基硅基化合物,反应式如下:
其中,R1和R2为氢原子、烷基、烷氧基或芳基,R1和R2相同或不同;
R3为烷基、烷氧基或芳基;
R4,R5和R6为烷基或芳基,R4,R5和R6相同或不同;
I为炔胺类化合物;
II为有机硅烷类化合物;
反应温度为25℃~65℃,反应时间为8h~24h,制备得到收率不低于65%的(Z)-β-型乙烯基硅基化合物。
2.根据权利要求1所述的新型乙烯基硅基化合物的制备方法,其特征在于,所述的炔胺类化合物与有机硅烷类化合物的摩尔比为1:2,炔胺类化合物的浓度为0.01-0.1mmol/ml。
3.根据权利要求1或2所述的新型乙烯基硅基化合物的制备方法,其特征在于,所述的[Rh(CO)2Cl]2的用量为炔胺类化合物的0.5~50mol%。
4.根据权利要求1或2所述的新型乙烯基硅基化合物的制备方法,其特征在于,所述的有机溶剂为乙腈、苯、甲苯、乙醚、甲基叔丁基醚、二氯甲烷、四氢呋喃、三氟甲苯、环己烷、石油醚中的一种或两种以上混合。
5.根据权利要求3所述的新型乙烯基硅基化合物的制备方法,其特征在于,所述的有机溶剂为乙腈、苯、甲苯、乙醚、甲基叔丁基醚、二氯甲烷、四氢呋喃、三氟甲苯、环己烷、石油醚中的一种或两种以上混合。
6.根据权利要求1、2或5所述的新型乙烯基硅基化合物的制备方法,其特征在于,所述的有机溶剂为乙腈、甲苯或氯仿。
7.根据权利要求3所述的新型乙烯基硅基化合物的制备方法,其特征在于,所述的有机溶剂为乙腈、甲苯或氯仿。
8.根据权利要求4所述的新型乙烯基硅基化合物的制备方法,其特征在于,所述的有机溶剂为乙腈、甲苯或氯仿。
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