CN107586296B - 2,9-二芳基取代的邻菲啰啉与其铁络合物的制备方法及其应用 - Google Patents
2,9-二芳基取代的邻菲啰啉与其铁络合物的制备方法及其应用 Download PDFInfo
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- 150000005041 phenanthrolines Chemical class 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 150000004698 iron complex Chemical class 0.000 title abstract description 5
- -1 aryl boric acid Chemical compound 0.000 claims abstract description 109
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 35
- 150000001336 alkenes Chemical class 0.000 claims abstract description 21
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 12
- 239000000654 additive Substances 0.000 claims abstract description 9
- 238000006069 Suzuki reaction reaction Methods 0.000 claims abstract description 8
- DNKGIDURJINUOA-UHFFFAOYSA-N 2,9-dichloro-1,10-phenanthroline Chemical compound C1=C(Cl)N=C2C3=NC(Cl)=CC=C3C=CC2=C1 DNKGIDURJINUOA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000000996 additive effect Effects 0.000 claims abstract description 6
- 239000004327 boric acid Substances 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910000077 silane Inorganic materials 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 51
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 35
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 28
- 229960002089 ferrous chloride Drugs 0.000 claims description 28
- 239000002904 solvent Substances 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- 125000001624 naphthyl group Chemical group 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 101150003085 Pdcl gene Proteins 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
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- 238000000034 method Methods 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
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- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 claims 1
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- 229910052742 iron Inorganic materials 0.000 abstract description 11
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- 230000000694 effects Effects 0.000 abstract description 6
- 238000010668 complexation reaction Methods 0.000 abstract description 2
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 22
- 238000005481 NMR spectroscopy Methods 0.000 description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 17
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 16
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- 239000000047 product Substances 0.000 description 14
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- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 description 10
- 238000000520 microinjection Methods 0.000 description 9
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000012295 chemical reaction liquid Substances 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 8
- 238000010898 silica gel chromatography Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 5
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000004809 thin layer chromatography Methods 0.000 description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- 229910021575 Iron(II) bromide Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 229940046149 ferrous bromide Drugs 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 3
- GKMOWWQAQRUQEL-UHFFFAOYSA-N C1=C(C=CC2=CC=CC=C12)C1=NC2=C3N=C(C=CC3=CC=C2C=C1)C1=CC2=CC=CC=C2C=C1 Chemical compound C1=C(C=CC2=CC=CC=C12)C1=NC2=C3N=C(C=CC3=CC=C2C=C1)C1=CC2=CC=CC=C2C=C1 GKMOWWQAQRUQEL-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
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- 238000011161 development Methods 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000002198 insoluble material Substances 0.000 description 3
- FZGIHSNZYGFUGM-UHFFFAOYSA-L iron(ii) fluoride Chemical compound [F-].[F-].[Fe+2] FZGIHSNZYGFUGM-UHFFFAOYSA-L 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
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- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- KIFZNYOOPWPAFI-UHFFFAOYSA-N (2,4,6-triethylphenyl)boronic acid Chemical compound CCC1=CC(CC)=C(B(O)O)C(CC)=C1 KIFZNYOOPWPAFI-UHFFFAOYSA-N 0.000 description 2
- WEEIKGRMZMXDCN-UHFFFAOYSA-N 2,9-dinaphthalen-1-yl-1,10-phenanthroline Chemical compound C1=CC=C2C(C3=CC=C4C=CC5=CC=C(N=C5C4=N3)C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 WEEIKGRMZMXDCN-UHFFFAOYSA-N 0.000 description 2
- HVCVRVKEIKXBIF-UHFFFAOYSA-N 2,9-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=C(C=CC=2C3=NC(=CC=2)C=2C=CC=CC=2)C3=N1 HVCVRVKEIKXBIF-UHFFFAOYSA-N 0.000 description 2
- IYKBMPHOPLFHAQ-UHFFFAOYSA-N 2-phenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=C(C=CC=2C3=NC=CC=2)C3=N1 IYKBMPHOPLFHAQ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 2
- 125000004423 acyloxy group Chemical group 0.000 description 2
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- 229910052736 halogen Inorganic materials 0.000 description 2
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- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 2
- YQTCQNIPQMJNTI-UHFFFAOYSA-N 2,2-dimethylpropan-1-one Chemical group CC(C)(C)[C]=O YQTCQNIPQMJNTI-UHFFFAOYSA-N 0.000 description 1
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
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- 238000004566 IR spectroscopy Methods 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
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- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical group C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
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- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- PGJLOGNVZGRMGX-UHFFFAOYSA-L iron(2+);trifluoromethanesulfonate Chemical compound [Fe+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F PGJLOGNVZGRMGX-UHFFFAOYSA-L 0.000 description 1
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- 125000005929 isobutyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])OC(*)=O 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005932 isopentyloxycarbonyl group Chemical group 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
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- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000005933 neopentyloxycarbonyl group Chemical group 0.000 description 1
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- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
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- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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Landscapes
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Catalysts (AREA)
Abstract
本发明涉及一种新型2,9‑二芳基取代的邻菲啰啉与其铁络合物的制备方法及其应用。具体的讲是以2,9‑二氯邻菲啰啉与芳基硼酸进行Suzuki偶联反应制备取代的邻菲啰啉,将其与铁盐进行络合反应,可以制备邻菲啰啉铁络合物。该邻菲啰啉铁络合物在添加剂存在下,能够催化多种烯烃或炔烃与硅烷的硅氢化反应,表现出很高的活性和选择性,特别是对于苯乙烯衍生物,1‑芳基丁二烯,1‑烷基‑1‑芳基丁二烯的硅氢化反应,给出和已知铁催化剂不同的马氏加成的选择性,对1,2‑二取代乙烯表现出优异的苄位选择性,具有很好的应用前景。
Description
技术领域
本发明涉及一种新型2,9-二芳基取代的邻菲啰啉与其铁络合物的制备方法及其应用。具体的讲是以2,9-二氯邻菲啰啉与芳基硼酸进行Suzuki偶联反应制备取代的邻菲啰啉,将其与铁盐进行络合反应,可以制备邻菲啰啉铁络合物。该邻菲啰啉铁络合物在添加剂存在下,能够催化多种烯烃或炔烃与硅烷的硅氢化反应,表现出很高的活性和选择性,特别是对于苯乙烯衍生物,1-芳基丁二烯,1-烷基-1-芳基丁二烯的硅氢化反应,给出和已知铁催化剂不同的马氏加成的选择性,对1,2-二取代乙烯表现出优异的苄位选择性,具有很好的应用前景。
背景技术
有机硅化合物广泛应用于工业、农业、医药等各大领域。过渡金属催化烯烃的硅氢化反应作为最重要、最基础的C-Si成键反应,具有优异的原子经济性,可以从大宗工业原料烯烃和硅烷出发合成有机硅化合物,为有机硅化学及有机硅材料的高速发展提供了有力支撑,是目前最大规模应用的均相催化之一,也一直是催化有机合成领域的研究重点和热点(Marciniec,B.;Gulinski,J.;Urbaniak,W.;Kornetka,Z.W.in Comprehensive Handbookon Hydrosilylation,Marciniec,B.Ed.;Pergamon,Oxford,2002,pp.3-7;Noels,A.F.;Hubert,A.J.in Industrial Applications of Homogeneous Catalysis,Mortreux,A.Ed.;Kluwer,Amsterdam,1985,pp.80-91)。
自第一例铂催化的烯烃硅氢化反应发现至今60多年来,人们发展了一系列过渡金属催化剂用于烯烃的硅氢化反应,但是目前应用于工业生产的主要是基于贵金属铂的催化剂。据统计,每年有数吨铂消耗于烯烃的硅氢化反应中,无法回收(Holwell,A.J.Platin.Met.Rev.2008,52,243)。由于铂是一种稀有金属,储量很低,价格昂贵且浮动大,大量使用时还会带来重金属的污染等问题,而且从反应性上来说,铂基催化剂还存在着选择性不理想、官能团耐受性差等问题,因此发展更经济、更绿色的烯烃硅氢化反应的催化剂成为该领域亟待解决的重要问题。
铁是地壳中储量最丰富的过渡金属,也是最廉价的金属,同时还有良好的生物兼容性,因此从可持续发展化学和绿色化学的角度来看,铁是最理想的催化剂。从化学性质上看,铁催化烯烃的硅氢化反应机理和贵金属可能不同,铁催化剂可能会在活性,选择性,官能团耐受性等方面为烯烃硅氢化反应带来新的契机。铁催化烯烃的硅氢化反应近年来受到广泛关注(Nakajima,Y.;Shimada,S.RSC Adv.2015,5,20603;Tondreau,A.M.;Atienza,C.C.H.;Weller,K.J.;Nye,S.A.;Lewis,K.M.;Delis,J.G.P.;Chirik,P.J.Science 2012,335,567)。但是目前文献中能够成功催化烯烃硅氢化反应的铁催化剂的种类还很少,并且存在诸如催化剂活性普遍不高,底物局限性大,官能团耐受性差,催化剂合成困难等问题。因此发展用于烯烃硅氢化反应的新型铁催化剂,克服已知催化剂存在的缺点,是本领域研究的重点之一。
发明内容
本发明的目的是提供一种2,9-二芳基取代邻菲啰啉与其铁络合物和制备方法及其应用,可以克服已有技术的缺点。
本发明所述的2,9-二芳基取代邻菲啰啉(I),其特征在于具有如下的结构式:
其中:R2、R3与R7、R8为并苯环,R1、R4、R5、R6、R9和R10为H,即2,9-双-2-萘基-1,10-菲啰啉;
R1、R3与R5为异丙基,R2、R4、R6、R7、R8、R8和R10为H,即2-(2,4,6-三异丙基)-苯基-9-苯基-1,10-菲啰啉;
R1、R3与R5为乙基,R6、R8与R10为异丙基,R2、R4、R7和R9为H,即2-(2,4,6-三异丙基)-苯基-9-(2,4,6-三乙基)-苯基-1,10-菲啰啉;
R1、R3、R5、R6、R8与R10为乙基,R2、R4、R7和R9为H,即2,9-双-2,4,6-三乙基苯基-1,10-菲啰啉;
R1、R3、R5、R6、R8与R10为异丙基,R2、R4、R7和R9为H,即2,9-双-2,4,6-三异丙基苯基-1,10-菲啰啉;
R1与R6为异丙基,R2、R3、R4、R5、R7、R8、R9和R10为H,即2,9-双-2-异丙基苯基-1,10-菲啰啉;
R2、R4、R7与R9为叔丁基,R1、R3、R5、R6、R8和R10为H,即2,9-双-3,5-二叔丁基苯基-1,10-菲啰啉;
R2、R4、R7与R9为苯基,R1、R3、R5、R6、R8和R10为H,即2,9-双-3,5-二苯基苯基-1,10-菲啰啉。
所述的2,9-二芳基取代邻菲啰啉的制备方法,其特征在于它是经过如下步骤制备:在甲苯与水的混合溶剂中,100~110℃下,PdCl2(dppf)为催化剂,Ba(OH)2为碱,2,9-二氯邻菲啰啉与芳基硼酸进行Suzuki偶联,反应10~48小时,制备得到2,9-二芳基邻菲啰啉,其反应式为:
或者在甲苯与水的混合溶剂中,100~110℃下,Pd(PPh3)4为催化剂,K3PO4为碱,2,9-二氯邻菲啰啉与芳基硼酸进行Suzuki偶联,反应10~48小时,制备得到2-芳基-9-氯邻菲啰啉,再在甲苯与水的混合溶剂中,100~110℃下,PdCl2(dppf)为催化剂,Ba(OH)2为碱,与芳基硼酸进行Suzuki偶联,反应10~48小时,制备得到2,9-二取代邻菲啰啉,其反应式为:
其中:R1~R10如上述化合物(I)所定义。
所述的2,9-二芳基取代邻菲啰啉铁络合物(II),其特征在于具有如下的结构式:
其中:R1~R10分别为H、C1~C8烷基、苯基、取代的苯基、萘基、取代的萘基;或R1~R5形成取代或非取代的并环或桥环、或R6~R10形成取代或非取代的并环或桥环;R1、R2、R3、R4、R5、R6、R7、R8、R9和R10可以相同,也可以不同;
所述取代的苯基或萘基、取代的并环或桥环中,取代基为C1~C8烷基、羟基、C2~C8酰氧基、卤素、氨基、(C1~C8酰基)氨基、二(C1~C8烷基)氨基、C1~C8酰基、C2~C8酯基、卤代烷基中的一种或几种;取代基数目为0~5;
X为卤素、C1~C8的羧酸根、硫酸根、高氯酸跟、四氟硼酸根或三氟甲磺酸根;
n=2,3。
所述的2,9-二芳基取代邻菲啰啉铁络合物(II),其特征在于:
所述的C1~C8烷基为甲基、乙基、正丙基、异丙基、环丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、新戊基、仲戊基、叔戊基、正己基、异己基、新己基、仲己基、叔己基、正庚基、异庚基、新庚基、仲庚基、叔庚基、正辛基、异辛基、新辛基、仲辛基或叔辛基;
所述的C1~C8酰基为甲酰基、乙酰基、丙酰基、正丁酰基、异丁酰基、正戊酰基、异戊酰基、仲戊酰基、新戊酰基、正己酰基、异己酰基、新己酰基、仲己酰基、正庚酰基、异庚酰基、新庚酰基、仲庚酰基、正辛酰基、异辛酰基、新辛酰基、仲辛酰基、1-环丙基甲酰基、1-环丁基甲酰基、1-环戊基甲酰基、1-环己基甲酰基、1-环庚基甲酰基;
所述的C2~C8酰氧基为乙酰氧基、丙酰氧基、正丁酰氧基、异丁酰氧基、正戊酰氧基、异戊酰氧基、仲戊酰氧基、新戊酰氧基、正己酰氧基、异己酰氧基、新己酰氧基、仲己酰氧基、正庚酰氧基、异庚酰氧基、新庚酰氧基、仲庚酰氧基、正辛酰氧基、异辛酰氧基、新辛酰氧基、仲辛酰氧基、1-环丙基甲酰氧基、1-环丁基甲酰氧基、1-环戊基甲酰氧基、1-环己基甲酰氧基、1-环庚基甲酰氧基;
所述的C2~C8酯基为甲氧羰基、乙氧羰基、丙氧羰基、异丙氧羰基、丁氧羰基、异丁氧羰基、正戊氧羰基、异戊氧羰基、新戊氧羰基、仲戊氧羰基、叔戊氧羰基、环戊氧羰基、正己氧羰基、异己氧羰基、新己氧羰基、仲己氧羰基、叔己氧羰基、环己氧羰基、正庚氧羰基、异庚氧羰基、新庚氧羰基、仲庚氧羰基、叔庚氧羰基、环庚氧羰基;
所述的卤代烷基为含氟、氯、溴或碘的卤代烷基。
所述的邻菲啰啉铁络合物(II),其特征在于它是:
2,9-双苯基-1,10-菲啰啉合氯化亚铁;
2,9-双-1-萘基-1,10-菲啰啉合氯化亚铁;
2,9-双-2-萘基-1,10-菲啰啉合氯化亚铁;
2,9-双-2,6-二乙基苯基-1,10-菲啰啉合氯化亚铁;
2-(2,4,6-三异丙基)-苯基-9-苯基-1,10-菲啰啉合氯化亚铁;
2-(2,4,6-三异丙基)-苯基-9-(2,4,6-三乙基)-苯基-1,10-菲啰啉合氯化亚铁;
2,9-双-2,4,6-三甲基苯基-1,10-菲啰啉合氯化亚铁;
2,9-双-2,4,6-三乙基苯基-1,10-菲啰啉合氯化亚铁;
2,9-双-2,4,6-三异丙基苯基-1,10-菲啰啉合氯化亚铁;
2,9-双-3,5-二叔丁基苯基-1,10-菲啰啉合氯化亚铁;
2,9-双-3,5-二三氟甲基苯基-1,10-菲啰啉合氯化亚铁;
2,9-双-3,5-二苯基苯基-1,10-菲啰啉合氯化亚铁;
2,9-双-2,4,6-三异丙基苯基-1,10-菲啰啉合溴化亚铁;
2,9-双-2,4,6-三异丙基苯基-1,10-菲啰啉合硫酸亚铁;
2,9-双-2,4,6-三异丙基苯基-1,10-菲啰啉合醋酸亚铁;
2,9-双-2,4,6-三异丙基苯基-1,10-菲啰啉合三氟甲磺酸亚铁;
2,9-双-2,4,6-三异丙基苯基-1,10-菲啰啉合三氯化铁;
2,9-双-3,5-二叔丁基苯基-1,10-菲啰啉合溴化亚铁;
2,9-双-3,5-二叔丁基苯基-1,10-菲啰啉合氟化亚铁;
2,9-双-3,5-二叔丁基苯基-1,10-菲啰啉合醋酸亚铁;
2,9-双-3,5-二叔丁基苯基-1,10-菲啰啉合三氯化铁。
所述的邻菲啰啉铁络合物(II)的制备方法,其特征在于它是经过如下步骤制备:在甲苯、苯、二甲苯、四氢呋喃、乙醚、1,4-二氧六环中的一种或几种有机溶剂中,0~140℃下,2,9-二芳基邻菲啰啉与相应的铁盐络合1~72小时,制备得到2,9-二芳基邻菲啰啉铁络合物,其反应式为:
其中:R1~R10、X、n如上述化合物(II)所定义。
所述的邻菲啰啉铁络合物(II)的应用,其特征在于它作为催化剂用于烯烃的硅氢化反应:
其中:[Fe]为权利要求3所述的邻菲啰啉铁络合物;R11~R14是C1~C8烷基、卤代烷基、苄基、苯乙基、苯乙烯基、取代苯乙烯基、苯基、取代的苯基、萘基、取代的萘基,R11、R12、R13、R14可以相同,也可以不同。
所述的邻菲啰啉铁络合物(II)的应用,其特征在于将催化剂加入反应瓶中,然后依次加入溶剂、硅烷、烯烃或炔烃底物和添加剂,在指定温度下搅拌反应至结束。
所述的邻菲啰啉铁络合物(II)的应用,其特征在于所述的硅氢化反应条件是:所用溶剂是C1~C8的醚类,甲苯或烷烃;催化剂用量为0.01~5mol%;底物浓度为0.001~10.0M;添加剂为格氏试剂、四氢铝锂、三乙基硼氢化钠、有机锂试剂中的一种或几种;反应温度为0~100℃;反应1~72小时。
总而言之,将2,9-二氯邻菲啰啉与芳基硼酸进行催化偶联,可以制备新型2,9-二芳基取代的邻菲啰啉;将取代的邻菲啰啉和铁盐进行络合,可以得到含不同阴离子的邻菲啰啉铁络合物。该新型邻菲啰啉铁络合物能够催化多种烯烃和炔烃的硅氢化反应,并表现出以下特点:底物适用范围很广,对1-芳基乙烯、1-烷基乙烯、环状烯烃、取代丁二烯、1,2-二取代乙烯、端炔、内炔都能给出很好的结果;对官能团的耐受性很好,卤素、烷氧基、芳氧基等取代基不影响反应结果;效率很高,转化数最高可达10000;特别是对于苯乙烯衍生物,1-芳基丁二烯,1-烷基-1-芳基丁二烯的硅氢化反应,给出和己知铁催化剂不同的马氏加成的选择性;对1,2-二取代乙烯表现出优异的苄位选择性。上述特点表明,本发明所提供的新型邻菲啰啉铁络合物催化剂克服了已有技术的缺点,是目前催化烯烃和炔烃硅氢化的最高效的铁催化剂之一,具有很好的应用前景。
具体实施方式
通过下述实施实例将有助于近一步理解本发明,但不应将此理解为本发明上述主题的范围仅限于以下的实施例,凡基于本发明上述内容所实现的技术均属于本发明的范围。
一般说明:
实施实例中使用了缩写,其含义如下:
Me是甲基,Et是乙基,iPr是异丙基,tBu是叔丁基,Ph是苯基,THF是四氢呋喃,DCM是二氯甲烷,DME是乙二醇二甲醚,PE是石油醚,EA是乙酸乙酯;dppf是1,1-双(二苯基膦)二茂铁
TLC是薄层色谱,NMR是核磁共振,HRMS是高分辨质谱,IR是红外吸收光谱;
所用溶剂在使用前用标准操作提纯,干燥:所用试剂均为市售或按照已有文献方法合成得到,并在使用前提纯。
实施例1:2,9-二芳基取代邻菲啰啉2a-2c的制备
在装有回流冷凝管、抽气头、橡胶塞的250mL两口瓶中依次称入反应物1(747mg,3mmol)、2,4,6-三乙基苯硼酸(1.86g,9mmol)、Ba(OH)2·8H2O(4.74g,15mmol)、PdCl2(dppf)(329mg,0.45mmol),真空线上将体系置换为氮气氛围,氮气流下加入脱气的甲苯(100mL)和水(5mL),开动搅拌,油浴升温至110℃。加热搅拌15h后,TLC确定反应物消耗完全,停止加热,冷却至室温。过滤除去不溶物,用40mL DCM洗涤残余物,滤液真空脱溶后,残余的棕黑色固体用100mL DCM溶解后转移到分液漏斗,饱和食盐水洗涤,无水硫酸钠干燥,有机相真空脱溶后干法上样柱层析(PE/EA=5∶1为淋洗剂),得目标产物2,9-双-2,4,6-三乙基苯基-1,10-菲啰啉(2a)(14.3g,2.8mmol),为白色固体。产率:95%;熔点:172-174℃。1H NMR(400MHz,CDCl3)δ8.27(d,J=8.2Hz,2H,Ar-H),7.87(s,2H,Ar-H),7.59(d,J=8.1Hz,2H,Ar-H),6.96(s,4H,Ar-H),2.64(q,J=7.4Hz,4H,Ar-2,6-CH2),2.39(m,8H,Ar-4-CH2),1.25(t,J=7.6Hz,6H,Ar-2,6-CH3),1.05(m,12H,Ar-4-CH3);13C NMR(101MHz,CDCl3)δ160.3,144.1,142.1,135.4,127.3,126.3,125.3,125.1,28.9,26.8,15.8,15.3;HRMS(ESI)calcdfor[M+H,C12H7Cl2N2]+:501.3270,Found 501.3266
以下化合物的合成方法与实施例1相同。
2,9-双-2,4,6-三异丙基苯基-1,10-菲啰啉(2b)
白色粉末,熔点:252-254℃,93%收率.1H NMR(400MHz,CDCl3)δ8.26(d,J=8.1Hz,2H,4,7-H),7.88(s,2H,5,6-H),7.59(d,J=8.1Hz,2H,3,8-H),7.05(s,4H,Ar-H),2.92(heptet,J=6.9Hz,2H,CH),2.50(heptet,J=6.9Hz,4H,CH),1.28(d,J=6.9Hz,6H,CH3),1.07(d,J=6.8,6H,CH3),1.06(d,J=6.9,6H,CH3);13C NMR(101MHz,CDCl3)δ160.6,148.6,146.3,146.1,137.0,135.2,127.2,126.2,125.0,120.6,34.4,30.524.1,24.0;HRMS(ESI)calcd for[M+H,C42H53N2]+:585.4209,Found 585.4208.
2,9-双-3,5-二叔丁基苯基-1,10-菲啰啉(2c)
白色粉末,熔点:268℃,90%收率。1H NMR(400MHz,CDCl3)δ8.30(d,J=8.4Hz,2H,4,7-H),8.07(m,6H),7.80(s,2H,5,6-H),7.55(t,J=1.7Hz,2H),1.44(s,36H,Me);13C NMR(101MHz,CDCl3)δ159.2,151.0,146.4,140.0,136.7,127.8,126.0,123.2,122.6,121.5,35.0,31.7.HRMS(ESI)calcd for[M+H,C42H53N2]+:557.3890,Found 557.3899.
实施例2:2,9-二芳基取代邻菲啰啉2d、2e的制备
在装有回流冷凝管、抽气头、橡胶塞的250mL两口瓶中依次称入反应物1(498mg,2mmol)、2,4,6-三异丙基苯硼酸(596mg,2.4mmol)、K3PO4·3H2O(2.66g,10mmol)、Pd(PPh3)4(346mg,0.3mmol),真空线上将体系置换为氮气氛围,氮气流下加入脱气的DME(70mL)和水(2.5mL),开动搅拌,油浴升温至95℃。加热搅拌15h后,TLC确定反应物消耗完全,停止加热,冷却至室温。过滤除去不溶物,用20mL DCM洗涤残余物,真空脱溶,残余物用50mL DCM溶解转移到分液漏斗,饱和食盐水洗涤,无水硫酸钠干燥,有机相真空脱溶后干法上样柱层析,得目标产物3(510mg,1.2mmol),为白色固体。产率:61%。1H NMR(400MHz,CDCl3)δ8.26(d,J=8.2Hz,1H,4-H),8.19(d,J=8.4Hz,1H,7-H),7.87(d,J=8.7Hz,1H,5-H),7.80(d,J=8.7Hz,1H,6-H),7.65(d,J=8.2Hz,1H,3-H),7.59(d,J=8.4Hz,1H,8-H),7.11(s,2H,Ar-H),2.96(heptet,J=6.8Hz,1H,Ar-4-CH),2.57(d,J=6.8Hz,2H,Ar-2,6-CH),1.30(d,J=6.7Hz,6H,Ar-4-CH3),1.18(d,J=6.8Hz,6H,Ar-2,6-CH31/2),1.11(d,J=6.9Hz,6H,Ar-2,6-CH31/2)。
在装有回流冷凝管、抽气头、橡胶塞的250mL两口瓶中依次称入反应物3(1.28g,3mmol)、2,4,6-三乙基苯硼酸(1.86g,9mmol)、Ba(OH)2·8H2O(4.74g,15mmol)、PdCl2(dppf)(329mg,0.45mmol),真空线上将体系置换为氮气氛围,氮气流下加入脱气的甲苯(100mL)和水(5mL),开动搅拌,油浴升温至110℃。加热搅拌15h后,TLC确定反应物消耗完全,停止加热,冷却至室温。过滤除去不溶物,用40mL DCM洗涤残余物,真空脱溶,残余物用100mL DCM溶解转移到分液漏斗,饱和食盐水洗涤,无水硫酸钠干燥,有机相真空脱溶后干法上样柱层析(PE/EA=10∶1为淋洗剂),得目标产物2d(1.38g,2.6mmol),为白色固体。产率:85%,熔点:164℃。1H NMR(400MHz,CDCl3)δ8.28(d,J=1.8Hz,1H,4-H),8.26(d,J=1.8Hz,1H,7-H),7.87(s,2H,5,6-H),7.61(d,J=8.1Hz,1H,3-H),7.57(d,J=8.1Hz,1H,8-H),7.05(s,2H,iPr-Ar-H),6.96(s,2H,Et-Ar-H),2.91(heptct,J=13.8,6.9Hz,1H,iPr-Ar-4-CH),2.64(q,J=7.6Hz,2H,Et-Ar4-CH2),2.56(heptet,J=13.6,6.8Hz,2H,iPr-Ar-2,6-CH),2.40-2.30(m,4H,Et-Ar-2,6-CH2),1.26(d,6H,iPr-Ar-4-CH3),1.25(t,3H,Et-Ar-4-CH3),1.10(d,J=4.9Hz,6H,iPr-Ar-2,6-CH31/2),1.08(d,J=4.9Hz,6H,iPr-Ar-2,6-CH31/2),1.00(t,J=7.6Hz,6H,Et-Ar-2,6-CH2);13C NMR(101MHz,CDCl3)δ160.6,160.3,148.7,146.4,146.3,146.1,144.1,142.0,137.9,137.1,135.5,135.3,127.3,127.3,126.3,125.3,125.1,125.0,120.7,34.5,30.5,28.9,26.7,24.2,24.1,15.7,15.3;HRMS(ESI)calcd for[M+H,C39H47N2]+:543.3739,Found 543.3739。
2-(2,4,6-三异丙基苯基)-9-苯基-1,10-菲啰啉(2e),合成方法与实施例2相同。
白色固体,产率:92%。熔点:262-263℃。1H NMR(400MHz,CDCl3)δ8.31(d,J=8.4Hz,1H,7-H),δ8.27(d,J=8.4Hz,2H,Ph-2,6-H),δ8.26(t,J=8.4Hz,1H,Ph-4-H),8.08(d,J=8.5Hz,1H,4-H),7.83(s,2H,5,6-H),7.65(d,J=8.2Hz,1H,8-H),7.49(t,J=7.2Hz,2H,Ph-3,5-H),7.43(d,J=6.7Hz,1H,3-H),7.16(s,2H,Ar-H),3.00(heptet,J=13.6,6.7Hz,1H,Ar-4-CH),2.70(heptet,J=13.4,6.8Hz,2H,Ar-2,6-CH),1.35(d,J=6.8Hz,6H,Ar-4-CH3),1.28(d,J=6.7Hz,6H,Ar-2,6-CH31/2),1.17(d,J=6.7Hz,6H,Ar-2,6-CH31/2);13C NMR(101MHz,CDCl3)δ146.76,136.66,135.23,129.20,128.71,127.97,127.77,126.09,125.15,120.91,120.39,34.42,30.64,24.64,24.25;HRMS(ESI)calcd for[M+H,C33H35N2]+:459.2800,Found 459.2798。
实施例3:2,9-二芳基取代邻菲啰啉铁络合物的制备
在手套箱中,在25mL反应瓶中称入2,9-双-2,4,6-三异丙基苯基-1,10-菲啰啉(2a)(1.001g,2mmol)和FeCl2(253.5mg,2mmol),加入20mL四氢呋喃,于室温下反应24小时后,真空泵抽走部分四氢呋喃(体系剩余约5mL),加入15mL正己烷后有橙红色固体析出,过滤,并用正己烷(3×5mL)洗涤滤饼,将所得固体收集,高真空泵抽干得目标产物2,9-双-2,6-二乙基苯基-1,10-菲啰啉合氯化亚铁(3a),橙色粉末,收率83%,分解温度282-286℃。1HNMR(400MHz,CDCl3)δ53.85(s,2H),27.88(s,2H),3.76(s,2H),1.87(s,2H),1.10(s,4H),0.27(s,6H),-3.58(s,12H),-10.77(s,4H),-12.86(s,4H),-16.74(s,2H).IR(neat):3555m,3481s,3416s,3237w,2967w,2933,2033w,1639m,1618m,1555w,1496w,917w,867w,760w,624.6cm-1.
以下化合物的合成方法与实施例3相同。
2,9-双-2,4,6-三异丙基苯基-1,10-菲啰啉合氯化亚铁(3b)
红色粉末,收率82%,分解温度:270-274℃。1H NMR(400MHz,CDCl3)δ54.62(s,2H),29.46(s,2H),2.43(s,4H),2.04(s,2H),1.26(s,12H),-6.0~-4.0(m,24H),-7.77(s,2H),-20.25(s,2H).IR(neat):3555m,3481s,3416s,3237w,2967w,2933,2033w,1639m,1618m,1555w,1496w,917w,867w,760w,624.6cm-1.
2,9-双-3,5-二叔丁基苯基-1,10-菲啰啉合氯化亚铁(3c)
橙黄色粉末,收率81%,分解温度286-288℃。1H NMR(400MHz,CDCl3)δ58.72(s,2H),3.55(s,2H),-0.11(s,36H),-13.71(s,2H),-20.75(s,2H).IR(neat):3524w,3436w,3306s,3210s,3961s,2905m,1667w,1629s,1552m,1496m,1416w,1363w,1250w,867m,754m,712m cm-1.
2,9-双-2,4,6-三甲基苯基-1,10-菲啰啉合氯化亚铁(3d)
橙黄色粉末,收率88%,分解温度:308-312℃。1H NMR(400MHz,CDCl3)δ53.01(s,2H),27.89(s,2H),1.63(s,4H),0.73(s,6H),-10.91(s,12H),-16.82(s,2H).IR(neat):3666w,3523w,2919m,1746s,1612m,1588s,1556m,1511s,1481s,1445m,1426m,1031m,897s,865m,760w,729w cm-1.
2,9-双苯基-1,10-菲啰啉合氯化亚铁(3e)
黄色粉末,收率88%,分解温度280-282℃。1H NMR(400MHz,CDCl3)δ58.38,27.13,2.38,0.77,1.26,-15.29.IR(neat)3645w,3301m,3207m,1728w,1584m,1548m,1507m,1446s,1420m,1356m,1322m,741s,700s cm-1.
下列化合物因顺磁性,无核磁表征数据:
2,9-双-1-萘基-1,10-菲啰啉合氯化亚铁(3f);
2,9-双-2-萘基-1,10-菲啰啉合氯化亚铁(3g);
2-(2,4,6-三异丙基)-苯基-9-苯基-1,10-菲啰啉合氯化亚铁(3h);
2-(2,4,6-三异丙基)-苯基-9-(2,4,6-三乙基)-苯基-1,10-菲啰啉合氯化亚铁(3i);
2,9-双-3,5-二三氟甲基苯基-1,10-菲啰啉合氯化亚铁(3j);
2,9-双-3,5-二苯基苯基-1,10-菲啰啉合氯化亚铁(3k)。
用含有不同阴离子的铁盐,按照实施例3的方法,可以合成含有不同阴离子的邻菲啰啉铁络合物。因产物具有顺磁性,无核磁表征数据。
2,9-双-2,4,6-三异丙基苯基-1,10-菲啰啉合溴化亚铁(3l);
2,9-双-2,4,6-三异丙基苯基-1,10-菲啰啉合硫酸亚铁(3m);
2,9-双-2,4,6-三异丙基苯基-1,10-菲啰啉合醋酸亚铁(3n);
2,9-双-2,4,6-三异丙基苯基-1,10-菲啰啉合三氟甲磺酸亚铁(3o);
2,9-双-2,4,6-三异丙基苯基-1,10-菲啰啉合三氯化铁(3p);
2,9-双-3,5-二叔丁基苯基-1,10-菲啰啉合溴化亚铁(3q);
2,9-双-3,5-二叔丁基苯基-1,10-菲啰啉合氟化亚铁(3r);
2,9-双-3,5-二叔丁基苯基-1,10-菲啰啉合醋酸亚铁(3s);
2,9-双-3,5-二叔丁基苯基-1,10-菲啰啉合三氯化铁(3t)。
实施例4:不同邻菲啰啉铁催化剂用于苯乙烯的硅氢化
在手套箱中称取催化剂3(0.0125mmol)于装有搅拌子的4mL反应瓶中,加入甲苯(1mL)后搅拌1min,用微量注射器称取苯乙烯(27.0mg,0.25mmol)和苯硅烷(29.8mg,0.275mmol)加入体系。搅拌下,用微量注射器加入EtMgBr(1.0M,in THF,27.5μL,0.0275mmol)后,立即加盖密封,置于电磁搅拌器上搅拌。于室温下反应10h后,将反应瓶取出手套箱,将反应液转移至圆底烧瓶中,旋蒸脱溶后,经硅胶柱层析(正己烷为洗脱液)得目标产物,为无色液体。1H NMR(400MHz,CDCl3)δ7.35-7.42(m,3H,Ar-H),7.22-7.33(m,4H,Ar-H),7.07-7.15(m,3H,Ar-H),4.28-4.35(m,2H,Si-H),2.57-2.67(m,1H,CH),1.45(d,J=7.7Hz,3H,CH3);13C NMR(101MHz,CDCl3)δ144.5(1C,Ar-C),135.6(2C,Ar-C),131.4(1C,Ar-C),129.7(1C,Ar-C),128.4(2C,Ar-C),127.8(2C,Ar-C),127.1(2C,Ar-C),125.0(1C,Ar-C),25.4(1C,CH),16.3(1C,CH3);29Si NMR(79MHz,CDCl3)δ-20.8.HRMS(EI)calcd for[M,C14H16Si]+:212.1021,Found 212.1023。所得实验结果见表1:
表1:不同邻菲啰啉铁络合物催化苯乙烯硅氢化的实验结果
实施例5:添加剂对反应的影响实验
在手套箱中称取催化剂3c(0.0125mmol)于装有搅拌子的4mL反应瓶中,加入甲苯(1mL)后搅拌1min,用微量注射器称取苯乙烯(27.0mg,0.25mmol)和苯硅烷(29.8mg,0.275mmol)加入体系。搅拌状态下,用微量注射器加入添加剂(0.0275mmol)后,立即加盖密封,置于电磁搅拌器上搅拌。于室温下反应10h后,将反应瓶取出手套箱,将反应液转移至圆底烧瓶中,旋蒸脱溶后,经硅胶柱层析(正己烷为洗脱液)得目标产物。所得实验结果见表2:
表2:添加剂对反应的影响
实施例6:不同溶剂中苯乙烯的催化硅氢化反应
在手套箱中称取催化剂3c(0.0125mmol)于装有搅拌子的4mL反应瓶中,加入溶剂(1mL)后搅拌1min,用微量注射器称取苯乙烯(27.0mg,0.25mmol)和苯硅烷(29.8mg,0.275mmol)加入体系。搅拌状态下,用微量注射器加入EtMgBr(1.0M,in THF,27.5μL,0.0275mmol)后,立即加盖密封,置于电磁搅拌器上搅拌。于室温下反应10h后,将反应瓶取出手套箱,将反应液转移至圆底烧瓶中,旋蒸脱溶后,经硅胶柱层析(正己烷为洗脱液)得目标产物。所得实验结果见表3:
表3:不同溶剂中苯乙烯催化硅氢化反应的实验结果
实施例7:邻菲啰啉铁络合物催化1-芳基乙烯的硅氢化
在手套箱中称取催化剂3c(0.01mmol)于装有搅拌子的4mL反应瓶中,加入溶剂(1mL)后搅拌1min,用微量注射器称取苯乙烯(0.5mmol)和苯硅烷(59.5mg,0.55mmol)加入体系。搅拌状态下,用微量注射器加入EtMgBr(1.0M,in THF,22μL,0.022mmol)后,立即加盖密封,置于电磁搅拌器上搅拌。于室温下反应10h后,将反应瓶取出手套箱,将反应液转移至圆底烧瓶中,旋蒸脱溶后,经硅胶柱层析(正己烷为洗脱液)得目标产物。所得实验结果见表4:
表4:邻菲啰啉铁络合物催化1-芳基乙烯的硅氢化结果
a使用5mol%3c及11mol%EtMgBr。
实施例8:邻菲啰啉铁络合物催化1-烷基乙烯的硅氢化
在手套箱中称取催化剂3b(0.01mmol)于装有搅拌子的4mL反应瓶中,加入甲苯(1mL)后搅拌1min,用微量注射器称取烯烃(0.5mmol)和苯硅烷(59.5mg,0.55mmol)加入体系。搅拌状态下,用微量注射器加入EtMgBr(1.0M,in THF,22μL,0.022mmol)后,立即加盖密封,置于电磁搅拌器上搅拌。于室温下反应10h后,将反应瓶取出手套箱,将反应液转移至圆底烧瓶中,旋蒸脱溶后,经硅胶柱层析(正己烷为洗脱液)得目标产物。所得实验结果见表5:
表5:邻菲啰啉铁络合物催化1-烷基乙烯的硅氢化结果
实施例9:邻菲啰啉铁络合物催化1-已烯的硅氢化
称取催化剂3b(0.7mg,0.001mmol)于装有搅拌子的15mL反应瓶中,加入甲苯(2mL)后搅拌1min,用微量注射器称取1-己烯(0.842g,10mmol)和苯硅烷(1.082mg,10mmol)加入体系。搅拌状态下,用微量注射器加入EtMgBr(1.0M,in THF,2.2μL,0.0022mmol)后,立即加盖密封,置于电磁搅拌器上搅拌。于室温下反应24h后,将反应瓶取出手套箱,将反应液转移至圆底烧瓶中,旋蒸脱溶后,经硅胶柱层析(正己烷为洗脱液)得目标产物1.8g g,98%产率。
实施例10:邻菲罗啉铁络合物催化1,2-二取代乙烯的硅氢化
在手套箱中称取催化剂3b(0.01mmol)于装有搅拌子的4mL反应瓶中,加入溶剂(1mL)后搅拌1min,用微量注射器称取烯烃(0.5mmol)和苯硅烷(59.5mg,0.55mmol)加入体系。搅拌状态下,用微量注射器加入EtMgBr(1.0M,in THF,22μL,0.022mmol)后,立即加盖密封,置于电磁搅拌器上搅拌。于室温下反应10h后,将反应瓶取出手套箱,将反应液转移至圆底烧瓶中,旋蒸脱溶后,经硅胶柱层析(正己烷为洗脱液)得目标产物。所得实验结果见表6:
表6:邻菲啰啉铁络合物催化环状烯烃的硅氢化结果
a使用5mol%3b及11mol%EtMgBr。
实施例11:邻菲啰啉铁络合物催化取代丁二烯的硅氢化
在手套箱中称取催化剂3d(0.01mol)于装有搅拌子的4mL反应瓶中,加入溶剂(1mL)后搅拌1min,用微量注射器称取二烯(0.5mmol)和苯硅烷(59.5mg,0.55mmol)加入体系。搅拌状态下,用微量注射器加入EtMgBr(1.0M,in THF,11μL,0.011mmol)后,立即加盖密封,置于电磁搅拌器上搅拌。于室温下反应10h后,将反应瓶取出手套箱,将反应液转移至圆底烧瓶中,旋蒸脱溶后,经硅胶柱层析(正己烷为洗脱液)得目标产物。所得实验结果见表7:
表7:邻菲啰啉铁络合物催化取代丁二烯的硅氢化结果
实施例12:邻菲罗啉铁络合物催化炔烃的硅氢化
在手套箱中称取催化剂3(0.0125mmol)于装有搅拌子的4mL反应瓶中,加入甲苯(1mL)后搅拌1min,微量注射器称取炔烃(26.0mg,0.25mmol)和苯硅烷(29.8mg,0.275mmol)加入体系。搅拌状态下,用微量注射器加入EtMgBr(1.0M,in THF,27.5μL,0.0275mmol)后,立即加盖密封,置于电磁搅拌器上搅拌。于室温下反应10h后,将反应瓶取出手套箱,将反应液转移至圆底烧瓶中,旋蒸脱溶后,经柱层析(正己烷为洗脱液)得目标产物,所得实验结果见表8:
表8:邻菲啰啉铁络合物催化炔烃的硅氢化结果
Claims (7)
1.一种2,9-二芳基取代邻菲啰啉,其特征在于具有如下的结构式:
其中:
R1、R3与R5为乙基,R6、R8与R10为异丙基,R2、R4、R7和R9为H,即2-(2,4,6-三异丙基)-苯基-9-(2,4,6-三乙基)-苯基-1,10-菲啰啉;
R1、R3、R5、R6、R8与R10为乙基,R2、R4、R7和R9为H,即2,9-双-2,4,6-三乙基苯基-1,10-菲啰啉;
R1、R3、R5、R6、R8与R10为异丙基,R2、R4、R7和R9为H,即2,9-双-2,4,6-三异丙基苯基-1,10-菲啰啉;
R2、R4、R7与R9为叔丁基,R1、R3、R5、R6、R8和R10为H,即2,9-双-3,5-二叔丁基苯基-1,10-菲啰啉。
2.权利要求1所述的2,9-二芳基取代邻菲啰啉的制备方法,其特征在于它是经过如下步骤制备:在甲苯与水的混合溶剂中,100~110℃下,PdCl2(dppf)为催化剂,Ba(OH)2为碱,2,9-二氯邻菲啰啉与芳基硼酸进行Suzuki偶联,反应10~48小时,制备得到2,9-二芳基邻菲啰啉,其反应式为:
或者在甲苯与水的混合溶剂中,100~110℃下,Pd(PPh3)4为催化剂,K3PO4为碱,2,9-二氯邻菲啰啉与芳基硼酸进行Suzuki偶联,反应10~48小时,制备得到2-芳基-9-氯邻菲啰啉,再在甲苯与水的混合溶剂中,100~110℃下,PdCl2(dppf)为催化剂,Ba(OH)2为碱,与芳基硼酸进行Suzuki偶联,反应10~48小时,制备得到2,9-二取代邻菲啰啉,其反应式为:
其中:R1~R10如权利要求1所定义。
6.按照权利要求5所述的应用,其特征在于将催化剂加入反应瓶中,然后依次加入溶剂、硅烷、烯烃或炔烃底物和添加剂,在0~100℃下搅拌反应至结束。
7.按照权利要求5所述的应用,其特征在于所述的硅氢化反应条件是:所用溶剂是C1~C8的醚类,甲苯或烷烃;催化剂用量为0.01~5mol%;底物浓度为0.001~10.0M;添加剂为格氏试剂、四氢铝锂、三乙基硼氢化钠、有机锂试剂中的一种或几种;反应温度为0~100℃;反应1~72小时。
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